CN107709029A

CN107709029A - Printing original plate, lithographic plate, printing discarded version and its layered product

Info

Publication number: CN107709029A
Application number: CN201680038902.1A
Authority: CN
Inventors: 岛中修知
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-06-30
Filing date: 2016-06-17
Publication date: 2018-02-16
Also published as: BR112018000045A2; EP3318414A4; WO2017002641A1; EP3318414A1; US20180117942A1; JPWO2017002641A1

Abstract

The present invention provides a kind of printing original plate, its side on supporter has the layer containing polymer, and have in opposite side containing the layer of metal oxide and particulate obtained from making organo-metallic compound or inorganic metal compound hydrolysis and polycondensation, in the printing original plate, when average grain diameter by the particulate is more than 0.3 μm and the printing original plate bigger than the thickness of the layer containing metal oxide and particulate is to be laminated printing original plate, even if linerless, it can also prevent the mutual bonding of master integrated displacement, master, abrade this three.

Description

Printing original plate, lithographic plate, printing discarded version and its layered product

Technical field

The present invention relates to a kind of printing original plate comprising original edition of lithographic printing plate and discarded plate originals, its layered product and Manufactured lithographic plate and printing discarded version, its layered product using printing original plate.

Background technology

Original edition of lithographic printing plate carries out keeping, transmitted often as multiple layered products for forming are superimposed.In the layered product, Generally to prevent the integrated displacement of original edition of lithographic printing plate, the mutual bonding of original edition of lithographic printing plate is prevented, prevents lithographic printing For the purpose of scratch of recording layer side surface of plate originals etc., lining paper is inserted between original edition of lithographic printing plate.But lining paper makes The problems such as cost increase, waste treatment being included with itself, and need to remove before exposure process, therefore turn into plate-making process Load, produce lining paper peel off bad error risk.Moreover, it is necessary to consider the note of original edition of lithographic printing plate when removing lining paper It is injury-free to record layer side surface.Accordingly it is desirable to research and develop the original edition of lithographic printing plate that can be laminated in a manner of linerless.

For example, as it is known that have it is a kind of in the face of the side opposite with the face with recording layer of supporter with containing the equal grains of number The original edition of lithographic printing plate (patent document 1) of the organic polymer layers of the polymer particle being crosslinked in 1~100 μm of footpath, set Have and be made up of and containing the delustering agent below 10 μm of average grain diameter the polymer emulsion below 40 DEG C of glass transition temperature (Tg) Back coating planographic printing plate material (patent document 2).And, it is known to a kind of one side in supporter has containing polymerization The photosensitive layer of thing particulate etc., and there is the lithographic printing of the back coating containing organic high molecular compound in the face of opposite side Plate originals (patent document 3).Moreover it is known that have as the superiors of the recording layer side of supporter and contain useful hydrophilic polymer Thing and silica cover the protective layer of the organic resin particulate on surface, and have in opposite side and include organic resin The original edition of lithographic printing plate (patent document 4) of back coating.

Conventional art document

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2007-148040 publications

Patent document 2：Japanese Unexamined Patent Publication 2006-56185 publications

Patent document 3：Japanese Unexamined Patent Publication 2008-249851 publications

Patent document 4：Japanese Unexamined Patent Publication 2008-15503 publications

The content of the invention

The invention technical task to be solved

However, in technology described in patent document 1, if specify that comprising cross-linking polymer particle and organic polymer Layer Tg it is too high, can not be substantially prevented from sometimes produce scratch.Also, it be specify that in known document 2 in described technology Sometimes the mutual bonding of master can not be substantially prevented from.Also, it be specify that in known document 3 in described technology in photosensitive layer In contain organic resin particulate, but photosensitive layer is the property for the lithographic plate for largely effecting on original edition of lithographic printing plate and being made from it Can layer, therefore the performance to original edition of lithographic printing plate, especially image formative do not have an impact, and particulate will not fall off as must Need part, in order that photosensitive layer has organic resin particulate, it is necessary to take into full account these performances, and the design model of photosensitive layer sometimes Enclose and be very limited.

Also, work as and technology described in known document 4 is applied to the thickness of protective layer than conventional wet developing type On the obvious thin machine of original edition of lithographic printing plate during developable original edition of lithographic printing plate etc., specify that can not obtain sufficient effect. Think the reason for this is that organic resin particulate is not kept fully, so as to cause from sag of protecting coating.

It is an object of the invention to provide a kind of printing original plate, wherein when stacking comprising original edition of lithographic printing plate and is discarded During the printing original plate of plate originals, even if linerless, it can also prevent the mutual bonding of master integrated displacement, master, abrade this Three.Also, it is an object of the invention to provide a kind of layered product of above-mentioned printing original plate.

Moreover, it is an object of the invention to provide a kind of lithographic plate or the discarded version of printing, it uses above-mentioned printing It is made of master.Also, it is an object of the invention to provide the stacking of a kind of above-mentioned lithographic plate or the discarded version of printing Body.

For solving the means of technical task

The present invention includes following structures.

1. a kind of printing original plate, its side on supporter has the layer containing polymer, and has in opposite side Contain the layer of metal oxide and particulate obtained from making organo-metallic compound or inorganic metal compound hydrolysis and polycondensation, institute State in printing original plate,

The average grain diameter of above-mentioned particulate is more than 0.3 μm, also, thicker than the above-mentioned layer containing metal oxide and particulate Degree is big.

2. the printing original plate according to 1., wherein,

Above-mentioned particulate is the particulate with hydrophilic surface.

3. the printing original plate according to 2., wherein,

The above-mentioned particulate with hydrophilic surface is selected from the organic resin particulate with hydrophilic surface, with hydrophily At least one of the inorganic particles on surface.

4. the printing original plate according to 3., wherein,

The above-mentioned organic resin particulate with hydrophilic surface is by selected from silica, aluminum oxide, titanium dioxide and oxygen Change the organic resin particulate of at least one of zirconium inorganic compound covering.

5. according to the printing original plate described in 3. or 4., wherein,

The above-mentioned organic resin particulate with hydrophilic surface is the organic resin particulate covered by silica.

6. the printing original plate according to any one of 3. to 5., wherein,

The organic resin for forming the above-mentioned organic resin particulate with hydrophilic surface is selected from polyacrylics, gathered Urethane based resin, polystyrene resins, polyester resin, epoxylite, phenolic resinoid and melamine tree At least one of fat resin.

7. the printing original plate according to any one of 1. to 6., wherein,

The above-mentioned layer containing polymer is the eurymeric image recording layer containing infrared absorbent.

8. the printing original plate according to any one of 1. to 6., wherein,

The above-mentioned layer containing polymer be containing infrared absorbent, polymerization initiator, polymerizable compound minus figure As recording layer.

9. the printing original plate according to any one of 1. to 6., wherein,

The above-mentioned layer containing polymer is containing infrared absorbent, polymerization initiator, polymerizable compound and microgranular The minus image recording layer of high-molecular compound.

10. the printing original plate according to any one of 1. to 6., wherein,

The above-mentioned layer containing polymer is to be recorded containing the minus image of infrared absorbent and particulate thermoplastic polymer Layer.

11. the printing original plate according to any one of claim 7. to 10., wherein,

The above-mentioned layer containing polymer can by printing-ink and fountain solution at least any one remove.

12. the printing original plate according to any one of 1. to 6., wherein,

The above-mentioned layer containing polymer is non-photosensitive layer.

13. the printing original plate according to 12., it is characterised in that

14. a kind of lithographic plate, it is made using the printing original plate any one of 1. to 11..

15. the discarded version of one kind printing, it is made using the printing original plate described in 12. or 13..

16. a kind of layered product, its printing original plate any one of 1. to 11. is directly contacted and be laminated multiple and Into.

17. a kind of layered product, it makes the printing original plate described in 12. or 13. directly contact and be laminated multiple to form.

18. a kind of layered product, it makes the lithographic plate described in 14. directly contact and be laminated multiple to form.

19. a kind of layered product, it makes the printing described in 15. directly be contacted with discarded version and be laminated multiple to form.

Moreover, the present invention also includes following structures.

20. a kind of method, image exposure is carried out to the printing original plate described in 11., supply printing-ink and fountain solution and The non-image portion of the above-mentioned layer containing polymer of image recording layer is removed on the printer, so as to be printed.

21. a kind of method, not carrying out image exposure to the printing original plate described in 12., printing-ink and fountain solution are supplied And the above-mentioned layer containing polymer is removed on the printer, so as to be printed.

Invention effect

In accordance with the invention it is possible to a kind of printing original plate is provided, wherein when stacking comprising original edition of lithographic printing plate and is discarded During the printing original plate of plate originals, even if linerless, it can also prevent the mutual bonding of master integrated displacement, master, abrade this Three.Also, the present invention can provide a kind of layered product of above-mentioned printing original plate.

Moreover, in accordance with the invention it is possible to provide a kind of lithographic plate or printing discarded version, it is used using above-mentioned printing Master and be made.Further, it is possible to provide a kind of layered product of above-mentioned lithographic plate or printing with discarded version.

Brief description of the drawings

Fig. 1 is the schematic diagram of one of the structure for the automatic developing device for representing original edition of lithographic printing plate.

Embodiment

The present invention is described in detail below.

In this specification, " printing original plate " this term includes original edition of lithographic printing plate and printing with discarded plate originals. Also, " galley " this term includes to be operated and manufactured lithographic plate through being exposed, develop to printing original plate etc. And the discarded version of printing.During for printing with discarded plate originals, the operation for exposing, developing not necessarily is needed.

Printing original plate involved in the present invention is following printing original plate, and its side on supporter has containing poly- The layer of compound, and opposite side have containing make organo-metallic compound or inorganic metal compound hydrolyze and polycondensation obtained from The layer of metal oxide and particulate, in the printing original plate, the average grain diameter of above-mentioned particulate is more than 0.3 μm, and than upper The thickness for stating the layer containing metal oxide and particulate is big.

The one of printing original plate involved in the present invention is characterised by, in the opposite with the layer containing polymer of supporter Side has containing metal oxide and tool obtained from making organo-metallic compound or inorganic metal compound hydrolysis and polycondensation There is the layer (below, also known as back coating) of the particulate of specific average grain diameter.

(back coating)

Back coating in printing original plate involved in the present invention, which contains, makes organo-metallic compound or inorganic metal chemical combination Metal oxide and particulate obtained from thing hydrolysis and polycondensation, the average grain diameter of above-mentioned particulate is more than 0.3 μm, and than above-mentioned The thickness of layer containing metal oxide and particulate is big.

(making metal oxide obtained from organo-metallic compound or inorganic metal compound hydrolysis and polycondensation)

Back coating, which includes, aoxidizes metal obtained from organo-metallic compound or inorganic metal compound hydrolysis and polycondensation Thing.

Contained gold obtained from making organo-metallic compound or inorganic metal compound hydrolysis and polycondensation in back coating Belong to oxide (following, also referred to as metal oxide), preferably make organo-metallic compound or inorganic metal compound in water And in organic solvent as obtained from the hydrolysis of the catalyst such as acid or alkali and condensation polymerization, so-called sol gel reaction liquid.

As organo-metallic compound or inorganic metal compound, for example, metal alkoxide, metal acetylacetonate can be enumerated Salt, metal acetate, metal oxalate, metal nitrate, metal sulfate, metal carbonate, metal oxychloride, metal chlorine Compound and by their locally hydrolysis and the condensation products that form of oligomerization.

Metal alkoxide is by formula M (OR)_n(in formula, M represents metallic element, and R represents alkyl, and n represents the oxidation of metallic element Number) represent compound.As concrete example, Si (OCH can be enumerated₃)₄、Si(OC₂H₅)₄、Si(OC₃H₇)₄、Si(OC₄H₉)₄、Al (OCH₃)₃、Al(OC₂H₅)₃、Al(OC₃H₇)₃、Al(OC₄H₉)₃、B(OCH₃)₃、B(OC₂H₅)₃、B(OC₃H₇)₃、B(OC₄H₉)₃、Ti (OCH₃)₄、Ti(OC₂H₅)₄、Ti(OC₃H₇)₄、Ti(OC₄H₉)₄、Zr(OCH₃)₄、Zr(OC₂H₅)₄、Zr(OC₃H₇)₄、Zr(OC₄H₉)₄ Deng in addition, the equiatomic alkoxide of Ge, Li, Na, Fe, Ga, Mg, P, Sb, Sn, Ta, V can be enumerated.Moreover, also it can be used CH₃Si(OCH₃)₃、C₂H₅Si(OCH₃)₃、CH₃Si(OC₂H₅)₃、C₂H₅Si(OC₂H₅)₃Etc. mono-substituted silicon alkoxide.

In organo-metallic compound or inorganic metal compound, the reactivity of metal alkoxide is enriched, and is easily formed by gold The polymer of the key composition of category-oxygen, therefore preferably.In these, Si (OCH₃)₄、Si(OC₂H₅)₄、Si(OC₃H₇)₄、Si(OC₄H₉)₄ Alkoxide cpd Deng silicon for low price and is readily available, and excellent from the spreadability of these obtained metal oxides, therefore especially Its is preferred.Also, the oligomer that further preferably alkoxide cpd of these silicon is locally hydrolyzed and is condensed.For example, it can enumerate SiO containing about 40 mass %₂Average 5 aggressiveness silester oligomer.

Organo-metallic compound or inorganic metal compound can be used singly or in combination two or more.

Moreover, it will further preferably substitute one of the tetraalkoxy compound of above-mentioned silicon with alkyl or with reactive group Or two alkoxies, so-called silane coupler and metal alkoxide use simultaneously.As silane coupler, can enumerate former with carbon Chain alkyl, the fluorine of subnumber 4~20 substitute the hydrophobic substituents such as alkyl to substitute one in the tetraalkoxy compound of above-mentioned silicon The silane coupler that individual or two alkoxies form, the particularly preferably silane coupler with fluorine substitution alkyl.It is even as silane Join the concrete example of agent, CF can be enumerated₃CH₂CH₂Si(OCH₃)₃、CF₃CF₂CH₂CH₃Si(OCH₃)₃、CF₃CH₂CH₂Si(OC₂H₅)₃Deng, In commercially available product, Shin-Etsu Chemical Co., Ltd. LS-1090 etc. can be enumerated.The content of silane coupler is preferably 5~90 mass % of the total solid content of back coating, more preferably 10~80 mass %.

As the catalyst of practicality when forming sol gel reaction liquid, organic, inorganic acid and alkali can be enumerated.As its example, Can enumerate the inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, hydrofluoric acid, phosphoric acid, phosphorous acid, formic acid, acetic acid, propionic acid, Butyric acid, glycolic, monoxone, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, bromoacetic acid, methoxyacetic acid, oxaloacetic acid, lemon Acid, oxalic acid, butanedioic acid, malic acid, tartaric acid, fumaric acid, maleic acid, malonic acid, ascorbic acid, benzoic acid, 3,4- dimethoxies The substituted benzoic acids such as yl benzoic acid, phenoxyacetic acid, phthalic acid, picric acid, nicotinic acid, pyridine carboxylic acid, pyrazine, pyrazoles, two Pyridine carboxylic acid, adipic acid, paratolunitrile, terephthalic acid (TPA), Isosorbide-5-Nitrae-cyclohexene -2,2- dicarboxylic acids, erucic acid, laurate, positive ten The alkali such as the hydroxide of the Organic Acid and Base such as one alkanoic acid metal and alkaline-earth metal, ammonia, monoethanolamine, diethanol amine, triethanolamine.

As other preferable catalyst, additionally it is possible to use sulphonic acids, sulfinic acid class, alkyl sulfide acids, phosphonic acid and phosphorus Esters of gallic acid etc., specifically, additionally it is possible to using p-methyl benzenesulfonic acid, DBSA, to toluenesulfinic acid, acetic acid, phenyl The organic acids such as phosphonic acids, phenyl phosphinic acid, phenyl phosphate, diphenyl phosphate.

Catalyst can be used singly or in combination two or more.On catalytic amount, relative to the metallization of raw material Compound, preferably 0.001~10 mass %, more preferably 0.05~5 mass %.If catalytic amount is the scope, well Trigger sol gel reaction, and suppress drastically to react, so as to prevent uneven sol-gel particle.

, it is necessary to appropriate water during initiation sol gel reaction.The addition of water is preferably the metallization of complete hydrolysis raw material 0.05~50 times mole of required amount, preferably 0.5~30 times mole during compound.If the amount of water is the scope, well It is hydrolyzed.

Solvent can be added in the reaction solution of sol-gel.As long as solvent dissolves to the metallic compound of raw material, and The solvent that the sol-gel particle generated in the reaction is dissolved or disperseed, and methanol, ethanol, third can be used The ketones such as the lower alcohols such as alcohol, butanol, acetone, methyl ethyl ketone, metacetone.Also, to improve the coated face quality of back coating Deng for the purpose of, glycols list or the dialkyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG can be used Ether or acetic acid esters.As solvent, the lower alcohols mixed with water are preferably able to.On sol gel reaction liquid, solvent adjustment is used Into the concentration of suitable coating, but if the total amount of solvent is added in reaction solution from the beginning, it is likely that because former Material is diluted and is difficult to hydrolysis.It is then preferred that a part for solvent is added in sol gel reaction liquid, and The method for adding remaining solvent when reacting and carrying out.

(particulate)

Back coating includes particulate.

Contained particulate is characterised by back coating, and average grain diameter is more than 0.3 μm, and than the thickness of back coating Greatly.

Particulate is preferably the particulate with hydrophilic surface.Particulate with hydrophilic surface is included with hydrophilic surface Organic resin particulate or with hydrophilic surface inorganic particles.

Organic resin particulate with hydrophilic surface is preferably by selected from silica, aluminum oxide, titanium dioxide and oxygen Change the organic resin particulate of at least one of zirconium inorganic compound covering.The organic resin particularly preferably covered by silica Particulate.

The organic resin for forming the organic resin particulate with hydrophilic surface is preferably selected from polyacrylics, gathered Urethane based resin, polystyrene resins, polyester resin, epoxylite, phenolic resinoid and melamine tree At least one of fat resin.

Hereinafter, organic resin particulate (following, organic tree also known as covered with silica to be covered by silica Fat particulate) exemplified by the organic resin particulate with hydrophilic surface is described in detail, but there is hydrophily in the present invention The organic resin particulate on surface is not limited to this.

(the organic resin particulate covered with silica)

Organic resin particulate covered with silica is to be formed with particulate of the silica covering comprising organic resin Particulate.Forming the organic resin particulate of core will not preferably be softened according to the moisture in air or temperature, or tacky.

As the organic resin for the organic resin particulate for forming the organic resin particulate covered with silica, such as can arrange Lift polyacrylics, polyurethanes resin, polystyrene resins, polyester resin, epoxylite, phenol Resin, melmac etc..

, can be excellent as the material of the silicon dioxide layer on the surface for forming organic resin particulate of the covering covered with silica Selection of land, which enumerates condensation product of oxyalkylsiloxane class compound etc., has the compound of alkoxysilyl, especially preferably Silicones are enumerated, specifically, it is preferable to enumerate silicon dioxide gel, cataloid, silica nanometer Silicon dioxide microparticles such as particle etc..

The structure of organic resin particulate covered with silica can be organic resin microparticle surfaces as solid into Point and be stained with the structure of silicon dioxide microparticle or make oxyalkylsiloxane class compound condensation react and in organic tree Fat microparticle surfaces form the structure of siloxane compound layer.

Silica will not necessarily cover the whole region of organic resin particle surface, if at least relative to organic resin The quality of particulate, surface is covered with more than 0.5 mass % amount, then can easily obtain the effect of the present invention.That is, in organic tree Silica be present at least a portion on the surface of fat particulate, thus, it is possible to realize in organic fine particles surface coexist it is water-soluble Property macromolecule, for example, raising with PVA compatibility, and come off even if by particulate is also suppressed in the case of external stress, And maintain excellent scoring resistance, resistance to caking property.Therefore, " covered with the silica " in the present invention is also included so organic The state of silica at least a portion on the surface of resin particle be present.

The surface covering state of silica can carry out morphologic observation and true by scanning electron microscope (TEM) etc. Recognize.Also, the overlay capacity of silica can detect Si atoms by using elementary analyses such as x-ray fluorescence analysis, and calculate The amount for the silica being present in Si atoms and confirmed.

There is no particular restriction for the manufacture method of organic resin particulate covered with silica, can make silica micro- The monomer component of the raw material of grain or silica precursor compound with turning into organic resin particulate coexists and to form organic resin micro- The method of silica surface coating is formed while grain, and can also be after organic resin particle is formed, by two Silicon oxide particle is physically adhered to surface, then the method for immobilization.

Hereinafter, enumerate the manufacture method of the organic resin particulate covered with silica 1.First, to comprising from poly- It is appropriate in inorganic suspending agent such as the water soluble polymers such as vinyl alcohol, methylcellulose, polyacrylic acid or calcium phosphate, calcium carbonate etc. The suspension stabilizer of selection water addition silica and material resin (more specifically, form above-mentioned organic resin, can The material resins such as the monomer of suspension polymerisation, the prepolymer for being capable of suspension crosslinking or resin liquid) and stir, mix and prepare and be dispersed with The suspension of silica and material resin.Now, species, its concentration, stirring number by adjusting suspension stabilizer etc., energy It is enough to form the suspension with target grain size.Then, the suspension is heated and makes its initiation reaction, and resin raw material is suspended Polymerization or suspension crosslinking and generate resin particle.Now, the silica coexisted is fixed on by polymerization or cross-linking reaction and solid The resin particle of change, especially because the physical property and be fixed on resin particle near surface.Then, solid-liquid point is carried out to suspension From, and the suspension stabilizer for being adhered to particle is cleaned and removes, and make its drying.Formed in this way, can obtain silica and fix Desired particle diameter the approximately spherical organic resin particulate covered with silica.

So, it is possible the control condition in suspension polymerisation or suspension crosslinking and obtain desired particle diameter covered with dioxy The organic resin particulate of SiClx, and having covered with silica can also be generated in the case where not carrying out this control tightly After machine resin particle, the organic fine particles covered with silica of desired size are obtained by screen filtration method etc..

The addition of the raw material in mixture during on manufacturing the organic fine particles covered with silica by the above method Amount etc., for example, when the total amount of material resin and silica is 100 parts by weight, first to the water 200 as decentralized medium~ 800 parts by weight add the parts by weight of suspension stabilizer 0.1~20, and fully dissolve or disperse, to putting into above-mentioned 100 weight in the liquid The material resin of part and the mixture of silica, while adjusting mixing speed in a manner of dispersed particle turns into designated size It is stirred, and liquid temperature is warming up to 30~90 DEG C after granularity adjustment has been carried out and reacted 1~8 hour.

On the manufacture method of the organic resin particulate covered with silica, above-mentioned method is its 1, such as can also Japanese Unexamined Patent Publication 2002-327036 publications, Japanese Unexamined Patent Publication 2002-173410 publications, Japanese Unexamined Patent Publication 2004- will enough be passed through The method recorded in detail in No. 307837 publications and Japanese Unexamined Patent Publication 2006-38246 publications etc. obtain covered with silica Organic resin particulate be preferably used in the present invention.

Also, the organic resin particulate covered with silica can also obtain as commercially available product, specifically, as Silica/melamine composite particles, Nissan Chemical Industries, Ltd. OPTBEADS can be enumerated 2000M、OPTBEADS 3500M、OPTBEADS 6500M、OPTBEADS 10500M、OPTBEADS 3500S、OPTBEADS 6500S.As silica/acrylic acid composite particles, Negami Chemical Industrial Co., Ltd systems can be enumerated ART PEARL G-200 are transparent, ART PEARL G-400 are transparent, ART PEARL G-800 are transparent, ART PEARL GR-400 It is transparent, ART PEARLGR-600 are transparent, ART PEARL GR-800 are transparent, ART PEARL J-7P.As silica/ammonia Carbamate composite particles, it is saturating that Negami Chemical Industrial Co., Ltd ART PEARLC-400 can be enumerated It is bright, C-800 is transparent, P-800T, U-600T, U-800T, CF-600T, CF800T, Dainichiseika Color＆ Chemicals Mfg.Co., Ltd. Dynamicbeads CN5070D, Danplacoat THU.

More than, by taking the organic resin particulate covered with silica as an example, to being made in back coating involved in the present invention Organic resin particulate is illustrated, but for being oxidized the organic resin particulate of aluminium, titanium dioxide or zirconium oxide covering, It can be implemented in an identical manner to use aluminum oxide, titanium dioxide or zirconium oxide by replacement of silicon dioxide.

As the inorganic particles with hydrophilic surface, the known inorganic particulate with hydrophilic surface can be used. Particularly preferably include the particulate of silica, aluminum oxide, zirconium oxide or titanium dioxide.

As particulate contained in back coating, additionally it is possible to use organic resin particulate., can be excellent as organic resin particulate Selection of land is enumerated including poly- (methyl) esters of acrylic acid, polystyrene and its derivative, polyamide-based, polyimide, low-density The particulate of the synthetic resin such as the TPOs such as polyethylene, high density polyethylene (HDPE), polypropylene, polyurethanes, polyureas, polyesters And particulate including natural polymers such as chitin, chitosan, cellulose, crosslinked starch, cross-linked celluloses etc..

Wherein, synthetic resin particulate, which has, is easily controlled particle size, and modified desired to be easily controlled by surface Surface characteristic the advantages that.

It is harder as polymethyl methacrylate (PMMA) in the manufacture method of this organic resin particulate During resin, additionally it is possible to by crush method and micronized, but easiness from size controlling, from the viewpoint of precision, preferably adopt With by emulsification/suspension polymerization and the method for compound particle.

The manufacture method of organic resin particulate is documented in association of " ultra micron and material " Japan material section and compiled in detail, Shokabo1993 is issued, and the spring horse supervision of " making and application of particulate, powder " Kawaguchi, CMC publish distribution in 2005 etc..

Organic resin particulate can also obtain as commercially available product, such as can enumerate Soken Chemical＆ Engineering Co., Ltd.s system, crosslinked acrylic resin MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-7G, MR-10G, MR-5C, MR-7GC, styrene resin lipid SX-350H, SX-500H, Sekisui Plastics Co., Ltd.s acrylic resin, MBX-5, MBX-8, MBX-12, MBX-15, MBX- 20、MB20X-5、MB30X-5、MB30X-8、MB30X-20、SBX-6、SBX-8、SBX-12、SBX-17、Mitsui Chemicals, Inc. vistanex, CHEMIPEARL W100, W200, W300, W308, W310, W400, W401, W405, W410, W500, WF640, W700, W800, W900, W950, WP100 etc..

Particulate used in back coating is preferably shaped to just spherical but it is also possible to be writing board shape or perspective view turn into The so-called spindle shape such as elliptical shape.

It is important that the average grain diameter of particulate is bigger than the thickness of back coating.The average grain diameter of particulate is thicker preferably than back coating Spend big more than 0.3 μm.

The average grain diameter of particulate is preferably 0.3~30 μm, more preferably 0.5~15 μm, more preferably 1~10 μm. It can show sufficient interval function in the scope, be easily fixed in back coating, and relative to the contact stress from outside With excellent holding function.

The average grain diameter of particulate in the present invention refers to commonly used volume average particle size, the volume average particle size It can be determined by laser diffraction/scattering formula particle size distribution meter.As measure device, such as particle size distribution dress can be enumerated Put " micro-trac MT-3300II " (Nikkiso Co., Ltd.s system).

The addition of the particulate covered with silica in back coating is preferably 5~1000mg/m², more preferably 10~ 500mg/m², more preferably 20~200mg/m²。

Can be as needed, other additives are added to back coating, for example, the fluorine of coating for improving back coating etc. Class surfactant, the other surfaces activating agent for adjusting slickness, the dyestuff or pigment for distinguishing for coloring edition species Deng.These additives are for example documented in (0030)~(0036) section of Japanese Unexamined Patent Publication 6-234284 publications in detail.

The thickness of back coating is preferably 0.01~30 μm, more preferably 0.1~10 μm, more preferably 0.2~5 μm. But the thickness of back coating should be more contained than in back coating above-mentioned particulate average grain diameter it is small.

The measure of the thickness of back coating can be carried out by following, i.e., be coated with the supporting body surface of back coating to be coated Back coating coating fluid and form back coating, with scanning electron microscope (SEM) observe back coating section and determine 5 at do not deposit In the thickness of the smooth region of particulate, and obtain its average value.

Back coating can be made by following, i.e., to containing above-mentioned metal oxide and particulate, and contain as needed The back coating coating fluid of other additives etc. is adjusted, and by back coating coating solution on supporter and dry.The back of the body applies Coating method known to rod coater coating etc. can be used in the coating of layer.Dry preferably 50~200 DEG C temperature, 10 seconds~ The time of 5 minutes or so.

[printing original plate]

Printing original plate involved in the present invention has the layer containing polymer in the side of supporter.

Hereinafter, the original edition of lithographic printing plate of the preferred embodiment as printing original plate is recorded.

[original edition of lithographic printing plate]

Original edition of lithographic printing plate involved in the present invention has image recording layer on supporter.In original edition of lithographic printing plate Image recording layer equivalent to the layer containing polymer in above-mentioned printing original plate.Image recording layer original edition of lithographic printing plate can So that there is priming coat between supporter and image recording layer as needed, and there is protective layer on image recording layer.

(image recording layer)

One preferred embodiment of image recording layer is that its non-image portion passes through acid~alkaline fountain solution and print on the printer At least one party of brush ink and the image recording layer being removed.

According to a mode, image recording layer is to contain infrared absorbent, polymerization initiator, polymerizable compound and bonding The minus image recording layer (following, also known as image recording layer A) of agent polymer.

According to another way, image recording layer is containing infrared absorbent, polymerization initiator, polymerizable compound and micro- The minus image recording layer (following, also known as image recording layer B) of granular high-molecular compound.

According to another mode, image recording layer is to be recorded containing the image of infrared absorbent and particulate thermoplastic polymer Layer (following, also known as image recording layer C).

(image recording layer A)

Image recording layer A contains infrared absorbent, polymerization initiator, polymerizable compound and binder polymer.With Under, image recording layer A constituent is illustrated.

Infrared absorbent, which has, to be converted to the function of heat by the infrared ray absorbed and is excited simultaneously by infrared ray To the function of polymerization initiator electronics described later movement and/or energy movement.Infrared absorbent used in the present invention is excellent Selecting has the dyestuff or pigment of maximum absorption, more preferably dyestuff under 760~1200nm of wavelength.

As dyestuff, can use described in (0082)~(0088) section of Japanese Unexamined Patent Publication 2014-104631 publications Dyestuff.

Preferably 0.01~1 μm, more preferably 0.01~0.5 μm of the particle diameter of pigment.During scattered pigment, it can be manufactured using ink Or the known dispersion technology used in toner manufacture etc..Detailed content is recorded in " newest pigment application technology ", and (CMC goes out Version, 1986 annuals) etc..

One kind can be used only in infrared absorbent can also be simultaneously using two or more.

The content of infrared absorbent relative to image recording layer the mass parts of total solid content 100, preferably 0.05~ 30 mass parts, more preferably 0.1~20 mass parts, especially preferably 0.2~10 mass parts.

Polymerization initiator is initiation and promotes the compound of the polymerization of polymerizable compound., can as polymerization initiator Use known thermal polymerization, the compound with the less key of bond dissociation energy, Photoepolymerizationinitiater initiater etc..Specifically, Radical polymerization described in (0092)~(0106) section of Japanese Unexamined Patent Publication 2014-104631 publications can be used to trigger Agent.

In polymerization initiator, as preferable compound, salt can be enumerated, wherein salt compounded of iodine and sulfosalt can be enumerated.Respectively From salt in (0104)~(0106) section of the preferable particular compound with Japanese Unexamined Patent Publication 2014-104631 publications in remembered The compound phase of load is same.

The content of polymerization initiator relative to image recording layer total solid content preferably 0.1~50 mass %, more preferably 0.5~30 mass %, particularly preferred 0.8~20 mass %.When can obtain better sensitivity and printing within the range The better resistance to soiling of non-image portion.

Polymerizable compound is the addition polymerization compound with least one ethylenical unsaturated double bonds, selected from extremely The compound of a few terminal ethylenic unsaturated bond, is preferably selected from the chemical combination with more than two terminal ethylenic unsaturated bonds Thing.These chemical forms such as with monomer, prepolymer, i.e. dimer, tripolymer and oligomer or their mixture. Specifically, polymerism described in (0109)~(0113) section of Japanese Unexamined Patent Publication 2014-104631 publications can be used Compound.

In above-mentioned, from the balanced excellent of the hydrophily relevant with developability on machine and the polymerizing power relevant with printing durability From the aspect of different, particularly preferred three (acryloyl-oxyethyl) isocyanuric acid ester, double (acryloyl-oxyethyl) ethoxys are different The ethylene-oxide-modified esters of acrylic acid of the isocyanuric acids such as cyanurate.

The structure of polymerizable compound, be used alone or use simultaneously, the detailed content of the application method of addition etc. can Arbitrarily set corresponding to the performance design of final original edition of lithographic printing plate.Polymerizable compound is relative to image recording layer Total solid content, preferably in 5~75 mass %, further preferably in 10~70 mass %, particularly preferably in 15~60 mass % In the range of use.

Binder polymer is mainly used for the purpose of the film-strength for improving image recording layer.Binder polymer can Use known polymer, the preferably polymer with film forming.Wherein, preferred acrylic resins, Pioloform, polyvinyl acetal Resin, polyurethane resin etc..

As preferable binder polymer, can enumerate as in Japanese Unexamined Patent Publication 2008-195018 publications it is described Main chain or side chain have the polymer of the cross-linking functional group for the film strength for being used to improve image portion, preferably have in side chain Polymer.Crosslinking is formed between polymer molecule by crosslinkable groups, and promotes to solidify.

As cross-linking functional group, preferably the olefinic insatiable hunger such as (methyl) acrylic, vinyl, pi-allyl, styryl With group or epoxy radicals etc., cross-linking functional group can be directed in polymer by high molecular weight reactive or combined polymerization.For example, energy Enough utilize has the reaction of the acrylate copolymer or polyurethane and GMA of carboxyl in side chain, or has The reaction of the carboxylic acids containing ethylenically unsaturated group such as the polymer and methacrylic acid of epoxy radicals.

The content of crosslinkable groups in binder polymer to every 1g binder polymers, preferably 0.1~ 10.0mmol, more preferably 0.25~7.0mmol, especially preferably 0.5~5.5mmol.

Also, binder polymer preferably has hydrophilic radical.Hydrophilic radical helps to assign to image recording layer Developability on machine.Especially, by making crosslinkable groups be coexisted with hydrophilic radical, it can have both and develop on printing durability and machine Property.

As hydrophilic radical, such as there are hydroxyl, carboxyl, oligoalkylene oxide structure, amino, ammonium, amide groups, sulfo group, phosphoric acid Base etc., wherein, the oligoalkylene oxide structure of the epoxy alkane unit preferably with 1~9 carbon number 2 or 3.Assigned to binder polymer When giving hydrophilic radical, such as can be by the way that the monomer copolymerizable with hydrophilic radical is carried out.

In order to control inking, the lipophilies such as alkyl, aryl, aralkyl, alkenyl can also be imported in binder polymer Group.For example, can be by the way that the monomer copolymerizable containing lipophilic group such as alkyl methacrylate be carried out.

The preferred matter average molecular weight of binder polymer (Mw) is 2, more than 000, more preferably 5, more than 000, further excellent Elect 10,000~300,000 as.

The content of binder polymer relative to the total solid content of image recording layer be 3~90 mass % be it is suitable, it is excellent Select 5~80 mass %, more preferably 10~70 mass %.

As the preference of binder polymer, the high-molecular compound that there is polyoxyalkylene chain in side chain can be enumerated.It is logical Cross and contain high-molecular compound (below, the also known as high-molecular compound of chain containing POA), the impregnability of fountain solution in image recording layer It is promoted, and developability is improved on machine, the high-molecular compound has polyoxyalkylene chain in side chain.

As the resin for the main chain for forming the high-molecular compound of chain containing POA, acrylic resin, Pioloform, polyvinyl acetal can be enumerated Resin, polyurethane resin, carbamide resin, polyimide resin, polyamide, epoxy resin, methacrylic resin, polyphenyl Vinyl resins, novolak type phenol resinoid, polyester resin, synthetic rubber, natural rubber, particularly preferred acrylic acid tree Fat.

The high-molecular compound of chain containing POA is the substantially compound not comprising perfluoroalkyl." substantially perfluor alkane is not included Base " is that as perfluoroalkyl, the mass ratio of existing fluorine atom is less than 0.5 mass % in high-molecular compound, is not preferably included Fluorine atom.The mass ratio of fluorine atom can be determined by elemental microanalysis method.

Also, the group that " perfluoroalkyl " is replaced by fluorine atoms for all hydrogen atoms of alkyl.

The alkylene oxide for being 2~6 as the preferably carbon number of the alkylene oxide (oxyalkylene) in polyoxyalkylene chain, more preferably ring Oxidative ethane (oxygen ethene) or expoxy propane (oxypropylene), further preferred oxirane.

The repeat number preferably 2~50, more preferably 4~25 of polyoxyalkylene chain, alkylene oxide in i.e. poly- (alkylene oxide) position.

The repeat number of alkylene oxide is more than 2, then can fully improve the impregnability of fountain solution, also, repeat number is less than 50, Then printing durability will not reduce because of abrasion, therefore preferably.

On poly- (alkylene oxide) position, preferably in (0060) of Japanese Unexamined Patent Publication 2014-104631 publications~(0062) section Described structure.

In order to improve the epithelium intensity of image portion, the high-molecular compound of chain containing POA can have bridging property.On with friendship The high-molecular compound of chain containing POA of connection property, it is documented in (0063)~(0072) section of Japanese Unexamined Patent Publication 2014-104631 publications In.

Relative to the total repeat unit for forming the high-molecular compound of chain containing POA, the repetition list with poly- (alkylene oxide) position The ratio of member is not particularly limited, preferably 0.5~80 mole of %, more preferably 0.5~50 mole of %.On the high score of chain containing POA The concrete example of sub- compound, it can enumerate in (0075)~(0076) section of Japanese Unexamined Patent Publication 2014-104631 publications described Compound.

The high-molecular compound of chain containing POA can be used in Japanese Unexamined Patent Publication 2008-195018 publications as needed and simultaneously The hydrophilic macromolecular compounds such as described polyacrylic acid, polyvinyl alcohol.Also, lipophile macromolecule can also be used simultaneously Compound and hydrophilic macromolecular compounds.

Form of the high-molecular compound of chain containing POA in image recording layer is as follows：Image recording layer is connected as playing The adhesive of the function of composition and exist, in addition, can also exist with particulate form.With situation existing for particulate form Under, average grain diameter is 10~1000nm scope, preferably 20~300nm scope, especially preferably 30~120nm model Enclose.

The content of the high-molecular compound of chain containing POA is relative to the total solid content of image recording layer, preferably 3~90 matter Measure %, more preferably 5~80 mass %.In the range of 3~90 mass %, it further can reliably have both the leaching of fountain solution Permeability and image formative.

As another preference of binder polymer, can enumerate with more officials more than 6 functions and below 10 functions Can mercaptan as core, and be bonded to by thioether bond the polymer chain of the core, and the polymer chain has the height of polymerizable group Molecular compound (below, also known as star gear transmission compound).As star gear transmission compound, such as can preferably use Described compound in Japanese Unexamined Patent Publication 2012-148555 publications.

On star gear transmission compound, it can enumerate in main chain or side chain, preferably there is such as Japanese Unexamined Patent Publication 2008- in side chain The described change for being used to improve the polymerizable groups such as the ethylenic unsaturated bond of film strength of image portion in No. 195018 publications Compound.Crosslinking is formed between polymer molecule by polymerizable group, and promotes solidification.

It is unsaturated as polymerizable group, the preferably olefinic such as (methyl) acrylic, vinyl, pi-allyl, styryl Group or epoxy radicals etc., from the viewpoint of polymerisation reactivity, more preferably (methyl) acrylic, vinyl, styryl, especially Its preferred (methyl) acrylic.These groups can be directed in polymer by high molecular weight reactive or combined polymerization.For example, energy It is enough using in the reaction of polymer of the side chain with carboxyl and GMA or the polymer with epoxy radicals With the reaction of the carboxylic acid containing ethylenically unsaturated group such as methacrylic acid.Those groups can use simultaneously.

The content of crosslinkable groups in star gear transmission compound is to every 1g star gear transmissions compound, and preferably 0.1 ~10.0mmol, more preferably 0.25~7.0mmol, most preferably 0.5~5.5mmol.

Also, star gear transmission compound preferably also has hydrophilic radical.Hydrophilic radical is helped beneficial to remembering to image Record developability on layer imparting machine.Especially, by making polymerizable group be coexisted with hydrophilic radical, printing durability can be had both and shown Shadow.

As hydrophilic radical ,-SO can be enumerated₃M¹、-OH、-CONR¹R²(M¹Represent hydrogen, metal ion, ammonium ion, Phosphonium from Son, R¹, R²Hydrogen atom, alkyl, alkenyl, aryl are represented independently of one another.R¹With R²It can be bonded and form ring.)、-N⁺R³R⁴R⁵X^- (R³~R⁵The alkyl of carbon number 1~8, X are represented independently of one another^-Represent counter anion), by following formulas (1) represent Group and the group represented by formula (2).

[chemical formula 1]

In above formula, n and m separately represent 1~100 integer, and R separately represents hydrogen atom or carbon number 1~18 alkyl.

Here, star gear transmission compound is to have polyoxyalkylene chain (for example, by above-mentioned formula (1) or (2) table in side chain The group shown) star gear transmission compound in the case of, this star gear transmission compound is in side chain to have above-mentioned polyoxy Change the high-molecular compound of alkene chain.

In these hydrophilic radicals, it is also preferred that-CONR¹R², by formula (1) represent group and by formula (2) represent base Group, more preferably-CONR¹R²And the group represented by formula (1), the group particularly preferably represented by formula (1).And by formula (1) in the group represented, more preferably n is 1~10, particularly preferred 1~4.Also, R more preferably hydrogen atoms or carbon number 1~4 Alkyl, particularly preferred hydrogen atom or methyl.These hydrophilic radicals can be simultaneously using two or more.

Also, star gear transmission compound is preferably substantially without carboxylic acid group, phosphate, phosphonate group.Specifically, it is excellent Choosing is less than 0.1mmol/g, more preferably less than 0.05mmol/g, especially preferably below 0.03mmol/g.These acidic groups are less than Developability is further enhanced during 0.1mmol/g.

Also, in order to suppress inking, the parents such as alkyl, aryl, aralkyl, alkenyl can be imported in star gear transmission compound Oiliness group.Specifically, by the monomer copolymerizable containing lipophilic group such as alkyl methacrylate.

As the concrete example of star gear transmission compound, can enumerate (0153) of Japanese Unexamined Patent Publication 2014-104631 publications Described compound in the section of~(0157).

In the case of above-mentioned multi-functional thiol's compound being present, star gear transmission compound can be by that will form polymer Method known to above-mentioned monomer free crowd of chain etc. synthesizes.

The matter average molecular weight of star gear transmission compound preferably 5,000~500,000, more preferably 10,000~250,000, Particularly preferred 20,000~150,000.Within the range, developability and printing durability become better on machine.

Star gear transmission compound can be used alone can also be used in mixed way it is two or more.And it is possible to leading to Normal straight chain type binder polymer uses simultaneously.

The containing ratio of star gear transmission compound is relative to the total solid content of image recording layer, preferably 5~95 mass %, More preferably below 10~90 mass %, particularly preferred below 15~85 mass %.

Especially, it is promoted from the impregnability of fountain solution, from the aspect of developability is improved on machine, preferably Japan is special Open star gear transmission compound described in 2012-148555 publications.

It can contain following described other compositions as needed in image recording layer A.

(1) the water-based compound of low molecular weight amphiphile

In order to not reduce printing durability and developability, image recording layer can contain low molecular weight amphiphile water-basedization on raising machine Compound.

As the water-based compound of low molecular weight amphiphile, such as water-soluble organic compounds, ethylene glycol, diethyl two can be enumerated The glycols such as alcohol, triethylene glycol, propane diols, DPG, tripropylene glycol and its ether or ester derivant class, glycerine, Ji Wusi The organic amines such as polyalcohols, triethanolamine, diethanol amine, the MEAs such as alcohol, three (2- ethoxys) isocyanuric acid esters and its The organic sulfamic acid class such as the organic sulfonic acid such as salt, alkyl sulfonic acid, p-methyl benzenesulfonic acid, benzene sulfonic acid class and its salt, alkyl amino sulfonic acid And its organic phosphine acids such as organic sulfuric acid such as salt, alkylsurfuric acid, alkyl ether sulfate and its salt, phenyl-phosphonic acid and its salt, winestone The organic carboxyl acid such as acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, amino acids class and its salt, betaines etc..

In these, preferably comprise in polyalcohols, organic sulfate class, organic sulfonic acid salt, the group of betaines It is at least one.

As the particular compound of organic sulfonate, can enumerate (0026) of Japanese Unexamined Patent Publication 2007-276454 publications~ (0031) compound described in section, (0020)~(0047) section of Japanese Unexamined Patent Publication 2009-154525 publications etc..Salt can be with For sylvite, lithium salts.

As organic sulfate, institute in (0034)~(0038) section of Japanese Unexamined Patent Publication 2007-276454 publications can be enumerated The compound of record.

As betaines, the compound that preferably carbon number for the hydrocarbon substituent of nitrogen-atoms is 1~5, as Concrete example, trimethyl ammonium acetate, dimethyl propyl ammonium acetate salt, 3- hydroxyl -4- trimethylammoniumbutyric acids salt, 4- (1- can be enumerated Pyridine radicals) butyrate, 1- hydroxyethyl -1- imidazoles acetate, trimethyl ammonium methane sulfonates, dimethyl propyl ammonium Loprazolam Salt, 3- trimethyl ammonium -1- propane sulfonates, 3- (1- pyridine radicals) -1- propane sulfonates etc..

The water-based compound of low molecular weight amphiphile is because the structure of hydrophobic parts is small, therefore fountain solution will not be impregnated with and be recorded in image Layer exposure portion (image portion) and reduce the hydrophobicity or film strength of image portion, and can maintain well image recording layer by Ink or printing durability.

0.5~20 mass % of the addition preferred image recording layer total solid content amount of the water-based compound of low molecular weight amphiphile. More preferably 1~15 mass %, further preferred 2~10 mass %.Developability and print on good machine are can obtain within the range Brush durability.

Compound can be used alone, and can also be used in mixed way two or more.

(2) grease agent is felt

In order to improve inking, in image recording layer can Shi phosphonium compounds, nitrogenous low molecular compound, gather containing ammonium Compound etc. feels grease agent.Especially, in the case of containing inanimate matter lamellar compound in protective layer, these compounds are as inanimate matter The surface dopant of lamellar compound and play function, and with preventing from printing the inking of midway because of inanimate matter lamellar compound Property reduce effect.

Phosphonium compounds, nitrogenous low molecular compound, the particular content containing Amino Polymer are documented in Japanese Unexamined Patent Publication 2014- In (0184) of No. 104631 publications~(0190) section.

The content of grease agent is felt relative to the total solid content of image recording layer, preferably 0.01~30.0 mass %, it is more excellent Select 0.1~15.0 mass %, further preferred 1~10 mass %.

(3) other compositions

Other compositions are used as in image recording layer, additionally it is possible to contain surfactant, colouring agent, print agent, Inhibition of polymerization Agent, advanced higher fatty acid derivative, plasticizer, inorganic particles, altogether inanimate matter lamellar compound, sensitizer, chain-transferring agent etc..Specifically For, can be preferably using (0114)~(0159) section of Japanese Unexamined Patent Publication 2008-284817 publications, Japanese Unexamined Patent Publication 2006- (0023) of No. 091479 publication~(0027) section, No. 2008/0311520 specification of U.S. Patent Publication (0060) section in institute The compound and addition of record.

Image recording layer A by forming as follows：For example, as Japanese Unexamined Patent Publication 2008-195018 publications (0142)~ (0143) it is described in section, necessary above-mentioned each composition is dispersed or dissolved in known solvent to prepare coating fluid, supported The coating fluid directly or across priming coat and by method known to rod coater coating etc. is coated and dried on body.Apply Image recording layer coating weight (solid constituent) on cloth, the supporter obtained after drying is different according to purposes, it is usually preferred to 0.3 ~3.0g/m².Within the range, it can obtain the good film forming characteristics of good sensitivity and image recording layer.

(image recording layer B)

Image recording layer B contains infrared absorbent, polymerization initiator, polymerizable compound and microgranular macromolecule chemical combination Thing.Hereinafter, image recording layer B constituent is illustrated.

On the infrared absorbent in image recording layer B, polymerization initiator and polymerizable compound, can equally use Described infrared absorbent, polymerization initiator and polymerizable compound in image recording layer A.

Microgranular high-molecular compound is preferably selected from particulate thermoplastic polymer, heat reactivity polymer particles, has and gather The polymer particles of conjunction property group, the microcapsules and microgel (cross-linked polymer particle) for including hydrophobic compound.Wherein, it is excellent Polymer particles and microgel of the choosing with polymerizable group.In especially preferred embodiment, microgranular high-molecular compound Including at least an olefinic unsaturation polymerizable group.Due to this microgranular high-molecular compound be present, can obtain improving exposure The effect of developability on the printing durability in light portion and the machine of unexposed portion.

As particulate thermoplastic polymer, Research Disclosure No.33303 in preferably in January, 1992, Japan Unexamined Patent 9-123387 publications, Japanese Unexamined Patent Publication 9-131850 publications, Japanese Unexamined Patent Publication 9-171249 publications, Japan are special Open particulate thermoplastic polymer described in No. 931647 specifications of flat 9-171250 publications and European Patent No. etc..

As form particulate thermoplastic polymer polymer concrete example, can enumerate ethene, styrene, vinyl chloride, Methyl acrylate, ethyl acrylate, methyl methacrylate, EMA, vinylidene chloride, acrylonitrile, ethene click The homopolymer of the monomers such as azoles, the acrylate with polyalkylene structure or methacrylate or copolymer or their mixing Thing.It is preferably able to enumerate polystyrene, the copolymer comprising styrene and acrylonitrile, polymethyl methacrylate.Thermoplastic poly Preferably 0.01~3.0 μm of the average grain diameter of compound particulate.Average grain diameter can be calculated by laser scattering method.

As heat reactivity polymer particles, the polymer particles with heat reactivity group can be enumerated.Heat reactivity gathers Functional group of the compound particulate by the crosslinking based on thermal response and now changes to form hydrophobization region.

, can if chemical bond can be formed as the heat reactivity group in the polymer particles with heat reactivity group Think the functional group for carrying out any reaction, preferably polymerizable group, as its example, preferably enumerate and carry out free crowd reaction Ethylenically unsaturated group (for example, acryloyl group, methylacryloyl, vinyl, pi-allyl etc.), cationic polymerizable group (for example, vinyl, ethyleneoxy, epoxy radicals, oxetanylmethoxy etc.), the NCO or its block for carrying out addition reaction Thing, epoxy radicals, ethyleneoxy and as these reaction object active hydrogen atom functional group (for example, amino, hydroxyl Base, carboxyl etc.), carry out condensation reaction carboxyl and as reaction object hydroxyl or amino, progress opening acid Acid anhydride and amino or hydroxyl etc. as reaction object.

As microcapsules, such as such as Japanese Unexamined Patent Publication 2001-277740 publications, Japanese Unexamined Patent Publication 2001-277742 publications In it is described, at least a portion of the constituent of image recording layer is included in microcapsules.The constituent of image recording layer is also It can contain outside microcapsules.The preferred embodiment of image recording layer containing microcapsules is following structure, i.e., is included in microcapsules thin Water-based constituent, and contain hydrophily constituent outside microcapsules.

Microgel (cross-linked polymer particle) can contain the structure of image recording layer at least one party on its surface or inside Into a part for composition.Especially, from the viewpoint of image forms sensitivity or printing durability, preferably have certainly on its surface By the reactive micro-gel of polymerizable group.

During by the constituent microencapsulation or microgel of image recording layer, known method can be applied.

Preferably 0.01~3.0 μm of the average grain diameter of microgranular high-molecular compound, more preferably 0.03~2.0 μm, further It is preferred that 0.10~1.0 μm.Within the range, good resolution ratio and ageing stability be can obtain.Average grain diameter can pass through laser Scattering method and calculate.

5~90 mass % of the content preferred image recording layer total solid content of microgranular high-molecular compound.

It can contain other compositions described in above-mentioned image recording layer A as needed in image recording layer B.

On image recording layer B formation, the record for forming above-mentioned image recording layer A can be applied.

(image recording layer C)

Image recording layer C contains infrared absorbent and particulate thermoplastic polymer.Hereinafter, to image recording layer C structure Illustrated into composition.

Infrared absorbent included in image recording layer C is preferably the dye for having in 760~1200nm maximum absorption Material or pigment.More preferably dyestuff.

As dyestuff, can utilize commercially available dyestuff and document (such as " dyestuff brief guide " Synthetic Organic Chemistry association edits, The annual of Showa 45, " chemical industry " in May, 1986 number " near infrared absorption pigment " P.45~51, " nineties is functional pigmented Exploitation and market trends " 2.3, the 2nd chapter (CMC publish, nineteen ninety periodical)) or Japan Patent in described known dyestuff. Specifically, preferably azo dyes, metallic complex salt azo dyes, pyrazolone azo dyes, anthraquinone dye, phthalocyanine dye, carbon The IR absorbing dyes such as dyestuff, quinoneimine dye, Polymethine dyes, cyanine dye.

In these, it is the infrared ray absorbing dye with water-soluble base to make an addition to especially preferred dyestuff during image recording layer Material.

The concrete example of IR absorbing dye described below, but the present invention is not limited to these.

[chemical formula 2]

[chemical formula 3]

As pigment, commercially available pigment and color index (C.I.) brief guide, " newest pigment brief guide " (Japanese face can be utilized Expect that technological associations compile, 1977 annuals), " newest pigment application technology " (CMC is published, 1986 annuals), " printing-ink technology " Described pigment in (CMC is published, 1984 annuals).

Preferably 0.01~1 μm, more preferably 0.01~0.5 μm of the particle diameter of pigment.As the method for scattered pigment, oil can be used Known dispersion technology used in ink manufacture or toner manufacture etc..Detailed content is recorded in " newest pigment application technology " (CMC is published, 1986 annuals).

0.1~30 mass % of the content preferred image recording layer solid constituent of infrared absorbent, more preferably 0.25~ 25 mass %, particularly preferred 0.5~20 mass %.Within the range, the film-strength of image recording layer will not be damaged and can obtain Good sensitivity.

Particulate thermoplastic polymer preferably its glass transition temperature (Tg) is 60 DEG C~250 DEG C.Thermoplastic polymer is micro- More preferably 70 DEG C~140 DEG C, further preferred 80 DEG C~120 DEG C of the Tg of grain.

It can be enumerated 1992 1 as the particulate thermoplastic polymer that Tg is more than 60 DEG C, such as preferable particulate Reseach Disclosure No.33303 of the moon, Japanese Unexamined Patent Publication 9-123387 publications, Japanese Unexamined Patent Publication 9-131850 Institute in publication, Japanese Unexamined Patent Publication 9-171249 publications, Japanese Unexamined Patent Publication 9-171250 publications and EP931647 publications etc. The particulate thermoplastic polymer of record.

Specifically, can illustrate by ethene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, metering system The monomers such as sour methyl esters, EMA, vinylidene chloride, acrylonitrile, vinyl carbazole form homopolymer or copolymer or Their mixture etc..As preferable compound, polystyrene, polymethyl methacrylate etc. can be enumerated.

If considering resolution ratio and ageing stability, the average grain diameter of particulate thermoplastic polymer is preferably 0.005~2.0 μm.The value be alternatively arranged as being mixed with two or more particulate thermoplastic polymers in the case of average grain diameter and apply.It is average Particle diameter is more preferably 0.01~1.5 μm, especially preferably 0.05 μm~1.0 μm.It is mixed with two or more thermoplastic polymers Polydispersity in the case of particulate is preferably more than 0.2.Average grain diameter and polydispersity can be calculated by laser scattering method.

Two or more particulate thermoplastic polymers can be used in mixed way.Specifically, can enumerate using particle size not At least two different situation of at least two same or use Tg.Two or more by being used in mixed way, the film forming of image portion is consolidated The property changed further improves, and in the case of lithographic plate, printing durability further improves.

For example, in the case of using particle size identical particulate as particulate thermoplastic polymer, it polymerize in thermoplasticity There can be a certain degree of hole between thing particulate, and even if making particulate thermoplastic polymer melting and solidification by image exposure, Sometimes film forming curability does not reach desired degree yet.In contrast, particle chi is used as particulate thermoplastic polymer In the case of very little different particulate, the porosity between particulate thermoplastic polymer can be reduced, as a result, image exposure can be improved The film forming curability of image portion afterwards.

Also, in the case of Tg identical particulates are used as particulate thermoplastic polymer, schemed by image exposure When not rising fully as the temperature of recording layer, the inabundant melting and solidification of particulate thermoplastic polymer and film forming curability is not up to sometimes To desired degree.In contrast, in the case of the different particulates of Tg are used as particulate thermoplastic polymer, even if logical Cross image exposure and the temperature of image recording layer does not rise fully, can also improve the film forming curability of image portion.

In the case of being used in mixed way the different particulate thermoplastic polymers of two or more Tg, at least one thermoplasticity polymerization The Tg of thing particulate is preferably more than 60 DEG C.Now, Tg difference is preferably more than 10 DEG C, more preferably more than 20 DEG C.Also, it is preferred that Contain the particulate thermoplastic polymer that Tg more than 70 mass % is more than 60 DEG C relative to all particulate thermoplastic polymers.

Particulate thermoplastic polymer can have crosslinkable groups.It is micro- using the thermoplastic polymer with crosslinkable groups Grain, crosslinkable groups thermal response and the formation crosslinking between polymer, image from there through caused heat in image exposure portion The film strength in portion is improved, and printing durability becomes more excellent.If chemical bond can be formed as crosslinkable groups, Can be the functional group for carrying out any reaction, for example, the ethylenically unsaturated group for carrying out polymerisation can be enumerated (for example, third Enoyl-, methylacryloyl, vinyl, pi-allyl etc.), carry out addition reaction NCO or its block thing and conduct It reacts the group (for example, amino, hydroxyl, carboxyl etc.) of the active hydrogen atom of object, similarly carries out addition reaction Epoxy radicals and react amino, carboxyl or the hydroxyl of object, the carboxyl for carrying out condensation reaction as it and hydroxyl or amino, opened The acid anhydrides and amino of cycloaddition reaction or hydroxyl etc..

As the particulate thermoplastic polymer with crosslinkable groups, specifically, acryloyl group, methyl-prop can be enumerated Enoyl-, vinyl, pi-allyl, epoxy radicals, amino, hydroxyl, carboxyl, NCO, acid anhydrides and protect these group etc. Particulate with crosslinkable groups.When these crosslinkable groups are imported into polymer, it can be carried out when polymer particles polymerize, It can also be carried out after polymer particles polymerization using high molecular weight reactive.

In the case of importing crosslinkable groups when polymer particles polymerize, preferred emulsion polymerization or suspension polymerisation have friendship The monomer of connection property group.Concrete example as the monomer with crosslinkable groups, allyl methacrylate, propylene can be enumerated Allyl propionate, vinyl methacrylate, vinyl acrylate, GMA, glycidyl acrylate, 2- isocyanatoethyls or blocked isocyanate based on its alcohol etc., 2- acrylic acid isocyano group ethyl esters or based on its alcohol Deng blocked isocyanate, 2- aminoethyl methacrylates, 2- aminoethyls acrylate, 2- hydroxyethyl methacrylates, 2- Hydroxy-ethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, 2 functional acrylates, 2 function methacrylates etc..

As the high molecular weight reactive utilized when carrying out the importing of crosslinkable groups after polymer particles polymerization, such as High molecular weight reactive described in No. WO96/34316 can be enumerated.

On particulate thermoplastic polymer, polymer particles can react via crosslinkable groups each other, can also be with The high-molecular compound or low molecular compound added in image recording layer reacts.

The content of particulate thermoplastic polymer is preferably 50~95 mass % of image recording layer solid constituent, and more preferably 60 ~90 mass %, particularly preferred 70~85 mass %.

Other compositions can be contained in image recording layer C as needed and also.

As the surfactant with polyoxyalkylenes (below, also referred to as POA yls) or hydroxyl, can suitably make With the surfactant with POA bases or hydroxyl, but preferred anionic surfactant or nonionic surfactant.Have In the anion surfactant or nonionic surfactant of POA bases or hydroxyl, the anionic surface preferably with POA bases is lived Property agent or nonionic surfactant.

As POA bases, preferably polyoxyethylene groups, polyoxypropylene base, polybutylene base etc., particularly preferred polyoxyethylene groups.

The average degree of polymerization of oxyalkylene group be usually 2~50 be it is suitable, preferably 2~20.

The number of hydroxyl be usually 1~10 be it is suitable, preferably 2~8.But the terminal hydroxyl in oxyalkylene group does not wrap It is contained in the quantity of hydroxyl.

(anion surfactant with POA bases or hydroxyl)

As the anion surfactant with POA bases, it is not particularly limited, polyoxyalkylene alkyl carboxylic acid can be enumerated Salt, polyoxyalkylene alkyl sulfosuccinic acid salt, polyoxyalkylene alkyl sulfuric ester salt, alkyl phenoxy polyoxygenated allyl Base Sulfonates, polyoxyalkylene alkyl sulphophenyl ethers, polyoxyalkylene aryl ether sulfuric ester salt, the polycyclic phenyl ether of polyoxyalkylene Sulfuric ester salt, polyoxyalkylene styrylphenyl ether sulfuric ester salt, polyoxyalkylene alkyl phosphates, polyoxyalkylene Alkyl phenyl ether phosphates, polyoxyalkylene perfluoroalkyl ethers phosphates etc..

As the anion surfactant with hydroxyl, it is not particularly limited, hydroxycarboxylic acid salt, hydroxyalkyl can be enumerated Ether carboxylate class, hydroxyalkylated sulfonic acid salt, glycerine monofatty ester sulfuric ester salt, glycerine monofatty ester phosphates Deng.

The content of surfactant with POA bases or hydroxyl is preferably 0.05~15 matter of image recording layer solid constituent Measure %, more preferably 0.1~10 mass %.

Hereinafter, the concrete example of the surfactant with POA bases or hydroxyl is enumerated, but the present invention is not limited to these. Following surfactant As -12 are ZONYL FSP ProductName and can obtained from Du Pont companies.Also, following surfaces are lived Property agent N-11 be ZONYL FSO 100 ProductName and can be obtained from Du Pont companies.

[chemical formula 4]

[chemical formula 5]

It can contain for the purpose of the uniformity of coating for ensuring image recording layer, in image recording layer and not have polyoxygenated The anion surfactant of alkenyl and hydroxyl.

As long as the anion surfactant can realize above-mentioned purpose, then there is no particular restriction.Wherein, preferred benzene sulfonamide Acid or its salt, alkyl naphthalene sulfonic acid or its salt, (two) alkyl diphenyl base ether (two) sulfonic acid or its salt, alkyl sulfate salt.

The addition of anion surfactant without polyoxyalkylenes and hydroxyl is relative to polyoxyalkylenes Or the surfactant of hydroxyl preferably 1~50 mass %, more preferably 1~30 mass %.

Hereinafter, the concrete example of the anion surfactant without polyoxyalkylenes and hydroxyl is enumerated, but the present invention is simultaneously It is not limited to those.

[chemical formula 6]

Also, for the purpose of the uniformity of coating for ensuring image recording layer, can use without polyoxyalkylenes and The nonionic surfactant or fluorine class surfactant of hydroxyl.For example, it is preferable to use institute in Japanese Unexamined Patent Application 62-170950 The fluorine class surfactant of record.

Image recording layer can contain hydrophilic resin.As hydrophilic resin, for example, preferably have hydroxyl, ethoxy, The resin of the hydrophilic radicals such as hydroxypropyl, amino, aminoethyl, aminopropyl, carboxyl, carboxylate group, sulfo group, sulfonic group, phosphate.

As the concrete example of hydrophilic resin, Arabic gum, casein, gelatin, starch derivatives, carboxymethyl can be enumerated Cellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic copolymer analog, styrene-maleic acid copolymerization Species, polyacrylic and its salt, polymethacrylic acid and its salt, the homopolymer of hydroxyethyl meth acrylate and copolymerization Thing, the homopolymer of hydroxy ethyl methacrylate and copolymer, the homopolymer of HPMA and copolymer, hydroxypropyl third The homopolymer and copolymer of olefin(e) acid ester, the homopolymer of hydroxyl butyl methyl acrylate and copolymer, hydroxyl butyl propyleneglycol acid esters it is equal Polymers and copolymer, polyethylene glycols, hydroxypropyl alkene polymer class, polyvinyl alcohol, degree of hydrolysis are at least 60%, are more preferably at least 80% hydrolysed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinylpyrrolidone, acrylamide Homopolymer and copolymer, the homopolymer of Methacrylamide and copolymer, the homopolymer of N hydroxymethyl acrylamide and copolymerization Thing etc..

From the viewpoint of it can obtain sufficient film strength and printing durability, the matter average molecular weight of hydrophilic resin is excellent Elect more than 2,000 as.

The content of hydrophilic resin is preferably 0.5~50 mass % of image recording layer solid constituent, more preferably 1~30 matter Measure %.

Image recording layer can contain inorganic particles., can be by silica, aluminum oxide, magnesia, oxygen as inorganic particles Change titanium, magnesium carbonate, calcium alginate or their mixture etc. to enumerate as preferable example.Inorganic particles can be to strengthen epithelium Used Deng for the purpose of.

Preferred 5nm~10 μm of average grain diameter of inorganic particles, more preferably 10nm~1 μm.Within the range, can be with thermoplastic Property polymer particles stably disperse, fully keep image recording layer film-strength, and formed be not likely to produce printing pollution and parent Water-based excellent non-image portion.

Inorganic particles can obtain as commercially available products such as cataloid dispersions.

The content of inorganic particles is preferably 1.0~70 mass % of image recording layer solid constituent, more preferably 5.0~50 matter Measure %.

In image recording layer, plasticizer can be contained in order to assign flexibility of film etc..As plasticizer, such as can Enumerate polyethylene glycol, ATBC, diethyl phthalate, dibutyl phthalate, DHP, Dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate etc..

The content of plasticizer is preferably 0.1%~50 mass % of image recording layer solid constituent, more preferably 1~30 matter Measure %.

In image recording layer, in the case of using the polymer particles with heat reactivity functional group (crosslinkable groups), The compound of the reaction of heat reactivity functional group (crosslinkable groups) can be added as needed on triggering or promoting.As trigger or Promote the compound of the reaction of heat reactivity functional group, can enumerate by heat to produce the chemical combination such as free radical or cation Thing.For example, it can enumerate comprising lophine dimer, trihalomethyl compound, peroxide, azo-compound, diazol, hexichol The salt of salt compounded of iodine etc., acylphosphanes, acid imide sulfonic acid etc..The addition of this compound is preferably image recording layer solid constituent 1~20 mass %, more preferably 1~10 mass %.Within the range, developability and it will not can be triggered or be promoted on infringement machine Enter the good effect of reaction.

Image recording layer C is formed as follows：Necessary above-mentioned each composition is dissolved or dispersed in appropriate solvent and applied to prepare Cloth liquid, and directly or it is coated with the coating fluid across priming coat on supporter.As solvent, water or water and organic solvent can be used Mixed solvent, but the planar after coating is made is from the aspect of good, is preferably used in mixed way water and organic solvent.It is organic molten The amount of agent is different according to the species of organic solvent, therefore can not clearly determine, is 5~50 appearances preferably generally in the mixed solvent Measure %.However, organic solvent needs to use with the amount of the UA scope of particulate thermoplastic polymer.Image recording layer is coated with The solid component concentration of liquid is preferably 1~50 mass %.

The organic solvent of solvent as coating fluid is preferably soluble in the organic solvent of water.Specifically, first can be enumerated The ketone solvents such as alcoholic solvent, acetone, the methyl ethyl ketones such as alcohol, ethanol, propyl alcohol, isopropanol, 1- methoxy-2-propanols, ethylene glycol two The glycol ether solvents such as methyl ether, gamma-butyrolacton, DMF, DMA, tetrahydrofuran, dimethyl Sulfoxide etc..Especially, preferably boiling point is less than 120 DEG C, and is 10g relative to the solubility (relative to water 100g meltage) of water Organic solvent above, more preferably more than 20g organic solvent.

As the coating method of image recording layer coating fluid, various methods can be utilized.For example, rod coater can be enumerated Coating, rotary coating, injection coating, curtain coating, dip coated, airblade coating, scraper plate coating, print roll coating etc..Coating, do The coating weight (solid constituent) of the image recording layer on supporter obtained after dry is different according to purposes, it is usually preferred to 0.5~ 5.0g/m², more preferably 0.5~2.0g/m²。

In the image recording layer of original edition of lithographic printing plate involved in the present invention, its non-image portion can pass through developer solution And the image recording layer being removed.This image recording layer is comprising public as so-called development treatment type original edition of lithographic printing plate The image recording layer for the most original edition of lithographic printing plate known.

According to by developer solution and the mode of image recording layer that is removed, image recording layer be containing sensitizing coloring matter, The minus image recording layer of polymerization initiator, polymerizable compound and binder polymer.This minus image recording layer is for example As<Recording layer>It is documented in (0057)-(0154) section of Japanese Unexamined Patent Publication 2008-15503 publications.

According to by developer solution and the mode of image recording layer that is removed, image recording layer be containing water-insoluble and The eurymeric image recording layer of alkali soluble resins and infrared absorbent.This eurymeric image recording layer is for example remembered as (recording layer) It is loaded in (0055)-(0132) section of Japanese Unexamined Patent Publication 2007-148040 publications.

Hereinafter, other constitutive requirements of original edition of lithographic printing plate are recorded.

(priming coat)

In original edition of lithographic printing plate, between image recording layer and supporter, priming coat can be arranged as required to.Primary coat Bonding of the layer due to strengthening supporter and image recording layer in exposure portion, and make it easy to remember from image in unexposed portion The supporter of record layer is peeling, so as to not damage printing durability and be favorably improved developability on machine.Also, infrared ray swashs In the case that light exposes, priming coat plays function as heat insulation layer, thus has by exposing and caused thermal diffusion in branch Support body and prevent sensitivity decline effect.

As the compound for being used in priming coat, specifically, institute in Japanese Unexamined Patent Publication 10-282679 publications can be enumerated Silane coupler, the Japanese Unexamined Patent Publication 2-304441 publications for the olefinic double bond reactive group with addition polymerizable recorded In the described phosphorus compound with olefinic double bond reactive group.As preferable compound, can enumerate such as Japanese Unexamined Patent Publication It is described such in 2005-125749 publications and Japanese Unexamined Patent Publication 2006-188038 publications, have adsorbable in support body surface The high-molecular compound of the adsorptivity group in face, hydrophilic radical and crosslinkable groups.As this high-molecular compound, preferably For the copolymer of the monomer with adsorptivity group, the monomer with hydrophilic radical and the monomer with crosslinkable groups.Enter One step specifically, can enumerate phenolic hydroxyl group, carboxyl ,-PO₃H₂、-OPO₃H₂、-CONHSO₂-、-SO₂NHSO₂-、-COCH₂COCH₃ Deng the monomer with hydrophilic radical such as the monomer with adsorptivity group, sulfo group and methacrylic acid group, pi-allyl etc. with The copolymer of the monomer of polymerizable crosslinkable groups.High-molecular compound can have to be substituted by the polarity of high-molecular compound The crosslinkable groups that base is formed and imported with the substituent with opposite charges and the salt of the compound with ethylenic unsaturated bond. And it is possible to further combined polymerization monomer other than the above, preferred hydrophilic monomer.

The content of unsaturated double-bond in priming coat high-molecular compound is to every 1g high-molecular compounds, and preferably 0.1 ~10.0mmol, more preferably 2.0~5.5mmol.

Priming coat is preferably 5, more than 000, more preferably 10 with the matter average molecular weight of high-molecular compound, and 000~300, 000。

,, can in order to prevent pollution over time in addition to above-mentioned priming coat compound in priming coat Contain chelating agent, secondary amine or tertiary amine, polymerization inhibitor, the functional group with amino or with Inhibition of polymerization energy and and aluminium support body Compound of group of surface interaction etc. is (for example, Isosorbide-5-Nitrae-diazabicylo [2,2,2] octane (DABCO), 2,3,5,6- tetra- Hydroxyl -1,4-benzoquinone, chloranil, sulfosalicylic phthalate, hydroxyethylethylene diamine tri-acetic acid, dihydroxy ethyl EDDA, hydroxyl second Base imido-acetic acid etc.).

Priming coat can be coated with by known method.Coating weight (solid constituent) preferably 0.1~100mg/ of priming coat m², more preferably 1~30mg/m²。

(supporter)

As the supporter of original edition of lithographic printing plate, known supporter can be used.Wherein, known method is preferably passed through It is roughened, and carries out the aluminium sheet of anodized.

On aluminium sheet, its appropriate selection can be handled as follows as needed, i.e. Japanese Unexamined Patent Publication 2001-253181 At the expansion processing of the micropore of anodic oxide coating described in publication or Japanese Unexamined Patent Publication 2001-322365 publications or sealing of hole Reason and based on such as U.S. Patent No. 2,714,066, U.S. Patent No. 3,181,461, U.S. Patent No. 3,280,734 and Described alkali silicate or such as U.S. Patent No. 3,276,868 in each specification of U.S. Patent No. 3,902,734 Number, polyvinyl phosphine described in each specification of U.S. Patent No. 4,153,461 and U.S. Patent No. 4,689,272 The surface hydrophilic processing of acid etc..

The center line average thickness of supporter is preferably 0.10~1.2 μm.

(protective layer)

In original edition of lithographic printing plate, protective layer can be set on image recording layer as needed.Protective layer is except passing through Resistance oxygen is formed beyond the function of hindering reaction to suppress image, and also having prevents from producing scar in image recording layer and prevent Gao Zhao The function of ablation when spending laser explosure.

On the protective layer with this function, can use (0202) of Japanese Unexamined Patent Publication 2014-104631 publications~ (0204) protective layer described in section.

Protective layer can be coated with by known method.The coating weight of protective layer is with dried coating gauge, preferably 0.01~10g/m², more preferably 0.02~3g/m², particularly preferred 0.02~1g/m²。

Original edition of lithographic printing plate can be coated with the coating of each structure sheaf by manufacture of such as getting off according to usual way Liquid, and dry and form each structure sheaf.Die coating methods, Dipcoat method, air knife coating method, curtain coating are used in coating Method, print roll coating method, bar rubbing method, gravure coating process, slidingtype rubbing method etc..

Hereinafter, the printing to another preferred embodiment as printing original plate is recorded with discarded plate originals.

Printing is (wherein, without figure for warp with original edition of lithographic printing plate identical plate-making process with discarded plate originals As exposure) and master of the printing with discarded version is made, substantially without photonasty.On printing with version is discarded, such as printing It is in field it is known that such, for example, being needed in colored newpapers and periodicals print (polychrome printing) with 2 colors or 1 color to a part of paper When face is printed, it is installed on plate cylinder and uses.

[the discarded plate originals of printing]

Printing involved in the present invention has non-photosensitive layer with discarded plate originals on supporter.Printing is former with discarded version Non-photosensitive layer in version is equivalent to the layer containing polymer in above-mentioned printing original plate.Printing can root with discarded plate originals There is priming coat between supporter and non-photosensitive layer according to needs, and there is hydrophilic layer on non-photosensitive layer.

One preferred embodiment of non-photosensitive layer is it on the printer by acid~alkaline fountain solution and printing-ink At least one party and the non-photosensitive layer that is removed.

Printing with discard plate originals in non-photosensitive layer preferably comprise water-soluble binder polymer or water-insoluble and Alkali-soluble binder polymer (it is following, also known as " binder polymer ".).Also, non-photosensitive layer can contain 350~ 550nm has the colouring agent and low molecule acid compound of maximum absorption.

Printing is for example documented in Japanese Unexamined Patent Publication 2011- with adhesive contained in the non-photosensitive layer in discarded plate originals In (0069) of No. 218778 publications-(0074) section.

Printing is for example documented in Japanese Unexamined Patent Publication 2011- with non-photosensitive layer in discarded plate originals and forming method thereof In (0021) of No. 218778 publications-(0054) section.

Hydrophilic layer of the printing in discarded plate originals contains adhesive.

The formation of hydrophilic layer can be formed by following, i.e., for example using 3,458, No. 311 specifications of U.S. Patent No. Or described method in Japanese Unexamined Patent Application 55-49729 publications, by adhesive and the colouring agent added according to purpose, The hydrophilic layer coating solution that the various additives such as water-soluble plasticizer, surfactant are stirred, mix and prepare is in non- On photosensitive layer.The coating weight of hydrophilic layer is preferably 0.2~5.0g/m², more preferably 0.3~3.0g/m²。

Printing is for example documented in Japanese Unexamined Patent Publication 2011- with adhesive contained in the hydrophilic layer in discarded plate originals In (0069) of No. 218778 publications-(0074) section.

Hereinafter, the plate-making to printing original plate involved in the present invention is recorded.Printing involved in the present invention is former The plate-making of version consists essentially of image exposure process and development treatment process.In addition, in printing original plate involved in the present invention, Printing carries out development treatment process with discarded plate originals without image exposure process.

(image exposure process)

The image exposure of original edition of lithographic printing plate can come according to the image exposure operation of common original edition of lithographic printing plate Carry out.

On image exposure, by the transparent artwork with line image, halftone dot image etc. and laser explosure or by based on Laser scanning of numerical data etc. is carried out.It is preferred that the wavelength of the light source using 700~1400nm.Light as 700~1400nm The Solid State Laser and semiconductor laser in source, preferably infrared radiation.On infrared laser, output is preferably more than 100mW, often The time for exposure of 1 pixel is preferably within 20 microseconds, and irradiation energy is preferably 10~300mJ/cm².During in order to shorten exposure Between, preferably using multibeam laser apparatus.Exposure mechanism can be any one in interior bulging mode, external drum mode, flatbed manner etc.. Image exposure can be carried out using plate forming machine etc. and by conventional method.

(development treatment process)

Development treatment can be carried out by usual way.When developing on machine, to the lithographic plate through image exposure Master, fountain solution and printing-ink is supplied on the printer, then in the exposure portion of image recording layer, by solidifying by exposure Image recording layer formed with lipophilic surface printing-ink receiving portion.On the other hand, in unexposed portion, pass through and supplied The fountain solution and/or printing-ink given, uncured image recording layer is removed by dissolving or disperseing, and hydrophilic surface It is exposed to the part.As a result, fountain solution is attached to the hydrophilic surface exposed, printing-ink inking is in the image of exposure area Recording layer and proceed by printing.

Here, the initially surface supply to original edition of lithographic printing plate can be that fountain solution can also be printing-ink, but In order that fountain solution is impregnated with and developability on promotion machine, preferred initial supply fountain solution.

It can be carried out using the development treatment of developer solution by conventional method.Development treatment type minus lithographic plate is former The development treatment of version is for example documented in (0197)-(0220) section of Japanese Unexamined Patent Publication 2008-15503 publications.Development treatment type The development treatment of eurymeric original edition of lithographic printing plate be for example documented in (0157) of Japanese Unexamined Patent Publication 2007-148040 publications- (0160) in section.

(printing original plate layered product, galley layered product)

Printing original plate layered product involved in the present invention is not across lining paper that printing involved in the present invention is former Version is directly laminated the layered product that multiple (being usually 2~500) form.

In printing original plate layered product involved in the present invention, due to possessed by printing original plate involved in the present invention The back coating of specific structure and any performance in landing property, caking property, scratch and impression is excellent, and will not produce integrated Displacement.

Galley layered product involved in the present invention is not divide lithographic plate or printing with discarded version across lining paper It is not laminated the layered product that multiple left and right form directly.On this layered product, after plate-making, until printing starts across several small When~several days or so when, by lithographic plate or printing with discarded version be laminated respectively multiple or so and be statically placed in appropriate position When formed.

In printing layered product involved in the present invention, due to specific possessed by printing original plate involved in the present invention The back coating of structure and any performance in landing property, caking property, scratch and impression is excellent, and be difficult to produce integrated position Move.

Embodiment

Hereinafter, by embodiment, the present invention is described in detail, but the present invention is not limited to these.In addition, high score In sub- compound, except not specially provided except, molecular weight is matter average molecular weight (Mw), the ratio of repeat unit for mole Percentage.Also, matter average molecular weight (Mw) is determines as based on the polystyrene scaled value of gel permeation chromatography (GPC) method Value.

[embodiment 101~114 and comparative example 101~107]

(making of original edition of lithographic printing plate 101)

The aluminium alloy plate of the composition shown in Table A to thickness 0.3mm implements following (a)~(m) processing, so as to make Supporter 1.In addition, implementing washing process between all treatment process, and carried out after washing process by roll Discharge opeing.

[table 1]

Table A

(a) mechanicalness roughening processing (brush grain method)

By ground pumice suspension (proportion 1.1g/cm³) as grinding milk and while supplied to surface of aluminum plate pass through rotation The clumps of bristles brush turned is handled to have carried out mechanicalness roughening.

In the processing of mechanicalness roughening, the median particle diameter of the ground pumice of grinding-material is set to 30 μm, by clumps of bristles brush Quantity is set to 4, and the rotating speed of clumps of bristles brush is set into 250rpm to carry out.The material of clumps of bristles brush is 610 nylon, bristle it is straight Footpath is 0.3mm, staple length 50mm.Clumps of bristles brush for the perforate in φ 300mm stainless steel cylinder and carry out plant hair make its change Close brush.The distance of 2 support rollers (φ 200mm) of clumps of bristles brush bottom is 300mm.Clumps of bristles brush, which is pressed into, makes brush The duty factor of the drive motor of rotation to aluminium sheet press clumps of bristles brush before the big 10kW of load untill.The rotation side of clumps of bristles brush To identical with the moving direction of aluminium sheet.

(b) alkali etching is handled

The mass % of caustic soda concentration 26, the matter of aluminium ion concentration 6.5 are blown to aluminium sheet by playpipe under temperature 70 C The causticity sodium water solution for measuring % has carried out etching process.Afterwards, washed by injection.Aluminium meltage is 10g/m²。

(c) abatement processes in acidic aqueous solution

Then, abatement processes have been carried out in aqueous solution of nitric acid.Aqueous solution of nitric acid used in abatement processes uses Subsequent processing it is Electrochemical roughening used in nitric acid electrolyte.Liquid temperature is 35 DEG C.By spray injection decontaminating liquid come The abatement processes of 3 seconds are carried out.

(d) Electrochemical roughening processing

Electrochemical roughening processing has been carried out continuously using 60Hz alternating voltage.Electrolyte has been used to temperature 35 DEG C, the nitric acid 10.4g/L aqueous solution addition aluminum nitrate aluminium ion concentration is adjusted to 4.5g/L electrolyte.AC power ripple Shape using current value from zero reach peak value untill time tp be 0.8msec, duty is than 1: 1, trapezoidal rectangular-wave alternating-current, and will Carbon electrode is used as to electrode to have carried out Electrochemical roughening processing.Impressed current anode has used ferrite.Current density is with electric current Peak value be calculated as 30A/dm², 5% electric current from power supply is shunted to impressed current anode.Electricity when electricity is using aluminium sheet as anode The summation of amount is calculated as 185C/dm².Washed afterwards by injection.

(e) alkali etching is handled

The mass % of caustic soda concentration 5, the mass % of aluminium ion concentration 0.5 are blown to aluminium sheet by playpipe under temperature 50 C Causticity sodium water solution carried out etching process.Afterwards, washed by injection.Aluminium meltage is 0.5g/m²。

(f) abatement processes in acidic aqueous solution

Then, abatement processes have been carried out in aqueous solution of nitric acid.Used in abatement processes sulfuric acid concentration 170g/L, aluminium from Sub- concentration 5g/L aqueous sulfuric acid.Liquid temperature is 60 DEG C.The abatement processes of 3 seconds have been carried out by spraying injection decontaminating liquid.

(g) Electrochemical roughening processing

Electrochemical roughening processing has been carried out continuously using 60Hz alternating voltage.Electrolyte has been used to liquid temperature 35 DEG C, the hydrochloric acid 6.2g/L aqueous solution addition salinization aluminium aluminium ion concentration is adjusted to 4.5g/L electrolyte.AC power ripple Shape using current value from zero reach peak value untill time tp be 0.8msec, duty is than 1: 1, trapezoidal rectangular-wave alternating-current, and will Carbon electrode is used as to electrode to have carried out Electrochemical roughening processing.Impressed current anode has used ferrite.Electrolytic cell has used Fig. 4 Shown electrolytic cell.Current density is calculated as 25A/dm with the peak value of electric current², when electricity in electrolysis of hydrochloric acid is using aluminium sheet as anode The summation of electricity is calculated as 63C/dm².Washed afterwards by injection.

(h) alkali etching is handled

The mass % of caustic soda concentration 5, the mass % of aluminium ion concentration 0.5 are blown to aluminium sheet by playpipe under temperature 50 C Causticity sodium water solution carried out etching process.Afterwards, washed by injection.Aluminium meltage is 0.1g/m²。

(i) abatement processes in acidic aqueous solution

Then, abatement processes have been carried out in aqueous solution of nitric acid.Use the sulfuric acid used in anodized process The aqueous solution (aluminium ion containing 5g/L in the sulfuric acid 170g/L aqueous solution), the abatement processes of 4 seconds are carried out at 35 DEG C of liquid temperature. The abatement processes of 3 seconds have been carried out by spraying injection decontaminating liquid.

(j) the 1st anodized

The anodized in the 1st stage has been carried out using the anodic oxidation device based on DC electrolysis.By shown in table B Condition carry out anodized, so as to form the anodic oxide coating of regulation leather film thickness.Bag has been used in electrolyte The aqueous solution of composition shown in B containing table.In table B~table D, described each composition in " constituent concentration " expression " solution composition " column Contain concentration (g/L).

[table 2]

Table B

(k) the 2nd anodized

The anodized in the 2nd stage has been carried out using the anodic oxidation device based on DC electrolysis.By shown in table C Condition carry out anodized, so as to form the anodic oxide coating of regulation leather film thickness.Bag has been used in electrolyte The aqueous solution of composition shown in C containing table.

[table 3]

Table C

(l) the 3rd anodized

The anodized in the 3rd stage has been carried out using the anodic oxidation device based on DC electrolysis.By shown in table D Condition carry out anodized, so as to form the anodic oxide coating of regulation leather film thickness.Bag has been used in electrolyte The aqueous solution of composition shown in D containing table.

[table 4]

Table D

(m) hydrophilicity-imparting treatment

In order to ensure the hydrophily of non-image portion, 7 are impregnated at 50 DEG C using 2.5 mass % No. 3 sodium silicate aqueous solutions Second implement silicic acid salt treatment.Si adhesion amount is 8.5mg/m².Afterwards, washed by injection.

The anodic oxide coating surface in the large diameter hole portion in the anodic oxide coating with micropore obtained by will be above-mentioned In average diameter (top layer average diameter), the average diameter (bottom average diameter) in the communicating position in large diameter hole portion, path Mean depth, the diameter holes of average diameter (path hole portion diameter), large diameter hole portion and path hole portion in the communicating position of hole portion The thickness (barrier layer thickness) of anodic oxide coating of the bottom in portion untill surface of aluminum plate, density of path hole portion etc. are shown in table E.Above-mentioned path hole portion includes different the 1st path hole portions and the 2nd path hole portion of depth, and a deeper side is referred to as into the 1st path Hole portion.

[table 5]

Table E (its 1)

[table 6]

Table E (its 2)

In table E, as barrier layer thickness, average value and minimum value are shown.Average value is as follows：Measure the 1st is small at 50 The thickness of anodic oxide coating of the bottom of footpath hole portion untill surface of aluminum plate, and carry out arithmetic mean and obtain.

The average diameter (average diameter of large diameter hole portion and path hole portion) of micropore is following value：With 150,000 times of multiplying power FE-SEM observations N=4 big footpath hole portion surfaces and path hole portion surfaces, in 4 resulting images, measure is present in 400 ×600nm²Scope micropore (large diameter hole portion and path hole portion) diameter, and be averaged and obtained.In addition, large diameter hole portion Depth it is deeper, and in the case of being difficult the diameter of measure path hole portion, cut anodic oxide coating top, obtain afterwards various Diameter.

The mean depth in large diameter hole portion is to observe cutting for supporter (anodic oxide coating) with the FE-TEM of 500,000 times of multiplying power Face, in resulting image, 60 (N=60) the arbitrary distance of micropore surface untill communicating position is determined, and carry out Value obtained from average.Also, the mean depth of path hole portion is by (50,000 times) observation supporter (anodic oxidations of FE-SEM Epithelium) section, in resulting image, determine the depth of any 25 micropores, and carry out it is average obtained from value.

" interconnecting part density " refers to, the density " surface area of the path hole portion in the anodic oxide coating section in communicating position Increase multiplying power " refers to, according to the value of following formula (A) calculating.

Formula (A)

Surface area increases multiplying power=1+ hole densities × ((π × (top layer average diameter/2+ bottoms average diameter/2) × ((bottom Portion's average diameter/2- top layers average diameter/2)²+ depth A²)^1/2+ π × (bottom average diameter/2)^2-π × (top layer average diameter/ 2)²))

In " mean depth (nm) " column of path hole portion, the mean depth of the 2nd path hole portion is shown in left side, and small by the 1st The mean depth of footpath hole portion is shown in right side.In " interconnecting part density " column of path hole portion in table E, by the close of the 1st path hole portion Degree and the interconnecting part density of path hole portion are together shown in bracket.

Also, positioned at the flat of the 1st path hole portion from the bottom of the 2nd path hole portion untill the bottom of the 1st path hole portion A diameter of 12nm or so.

(preparation of back coating coating fluid (1))

If mentioned component is mixed, stirred, started to generate heat at about 5 minutes.After reaction 60 minutes, pass through addition Solution as shown below and be prepared for back coating coating fluid (1).It is in addition, anti-and what is generated by the mixing of mentioned component, stirring Answer in table F~I that product discloses below and be expressed as metal oxide 1.

On a surface of supporter 1, the back coating coating fluid (1) of above-mentioned composition is subjected to rod painting, dried at 100 DEG C 120 seconds and form the back coating of 1.5 μm of thickness.

On another surface of supporter 1, the priming coat coating fluid (1) of following compositions is turned into 20mg/ with drying coated amount m²Mode be coated, so as to form priming coat.

(priming coat coating fluid (1))

[chemical formula 7]

On priming coat, after the image recording layer coating fluid (1) of following compositions is carried out into rod painting, dried at 100 DEG C 60 seconds, so as to form drying coated amount 1.0g/m²Image recording layer.

Image recording layer coating fluid (1) before it will be coated with by being mixed and stirred for following photosensitive liquids (1) and microgel Liquid (1) obtains.

(image recording layer coating fluid (1))

(photosensitive liquid (1))

Three (acryloyl-oxyethyl) isocyanuric acid esters

(NK esters A-9300, Shin-Nakamura Chemical Co., Ltd.s system)

Anionic surfactant 1 (following structures) 0.050g

Feel grease agent 0.055g

Phosphonium compounds (1) (following structures)

Feel grease agent 0.018g

Benzyl dimethyl octyl group ammonium PF₆Salt

Feel grease agent 0.040g

Containing Amino Polymer (following structures)

(Mw：50,000, reduced specific viscosity 45ml/g)

Fluorine class surfactant (1) (following structures) 0.008g

2- fourth copper 1.091g

1- methoxy-2-propanols 8.609g

(microgel liquid (1))

Microgel (1) 2.640g

Distilled water 2.425g

[chemical formula 8]

[chemical formula 9]

(making of microgel (1))

As oil-phase component, polyfunctional isocyanate's (Mitsui Chemicals, Inc. systems of the following structures of addition；75 Quality % ethyl acetate solution) 4.46g, trimethylolpropane (6 moles) and XDI (18 moles), and it is right The single-ended last polyoxyethylene of these addition methyl (1 mole, the repeat number of oxygen ethylene unit：90) addition product (Mitsui formed Chemicals Polyurethanes Inc. systems；50 mass % ethyl acetate solution) 10g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.s system, SR444) 3.15g and PIONIN A-41C (Takemoto Oil＆Fat Co., Ltd.s System) 0.1g is dissolved in ethyl acetate 17g.Polyvinyl alcohol (Kuraray Co., Ltd.s system, PVA- are prepared for as water-phase component 205) 4 mass % aqueous solution 40g.Oil-phase component and water-phase component are mixed, and emulsified using harmonious material device with 12,000rpm 10 minutes.Resulting emulsion is made an addition to 25g distilled water, is stirred at room temperature after 30 minutes, is stirred at 50 DEG C 3 hours.It is diluted using distilled water so that the solid component concentration of so obtained microgel liquid turns into 15 mass %, So as to make microgel (1).Average grain diameter by the microgel of light scattering determining is 0.2 μm.

[chemical formula 10]

On image recording layer, after protective layer coating solution (1) rod of following compositions is applied, dried 60 seconds at 120 DEG C, And form drying coated amount 0.15g/m²Protective layer made original edition of lithographic printing plate 101.

(protective layer used coating fluid (1))

Inorganic layered compounds dispersion liquid (1) (following) 1.5g

Hydrophilic polymer (1) (following structures, Mw：30,000) (solid constituent) 0.03g

Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd.s system, CKS50,

0.10g

Sulfonic acid modified, 99 moles of more than % of saponification degree, the degree of polymerization 300) the 6 mass % aqueous solution

Polyvinyl alcohol (Kuraray Co., Ltd.s system, PVA-405,81.5 moles of % of 0.03g saponification degrees, the degree of polymerization 500) the 6 mass % aqueous solution

Surfactant (EMALEX710, Nihon Emulsion Co., Ltd.s system) 0.86g

(following structures) 1 mass % aqueous solution

Ion exchange water 6.0g

[chemical formula 11]

(preparation of inorganic layered compounds dispersion liquid (1))

To ion exchange water 193.6g addition synthetic mica SOMASIF ME-100 (Co-op Chemical Co., Ltd.s System) 6.4g, volume average particle size (laser scattering method) is dispersed to as 3 μm using harmonious material device.Resulting dispersed particle is indulged Horizontal ratio is more than 100.

(making of original edition of lithographic printing plate 102~111)

In the making of original edition of lithographic printing plate 101, to the gold in back coating coating fluid as shown in following table F Species, the species of particulate, average grain diameter and the thickness of addition and back coating of category oxide are changed, in addition, Original edition of lithographic printing plate 102~111 has been made in an identical manner.

(making of original edition of lithographic printing plate 112)

The priming coat of the supporter with back coating and priming coat used in the making of original edition of lithographic printing plate 1 On, after image recording layer coating fluid (2) rod of following compositions is applied, dried 60 seconds at 70 DEG C, so as to form drying Coating weight 0.6g/m²Image recording layer.In this way, original edition of lithographic printing plate 112 is made.

(image recording layer coating fluid (2))

It is for example following with the compound that the ProductName in above-mentioned form is recorded.

·IRGACURE 250：(4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl] iodine=hexafluorophosphate (75 matter Measure % carbonic allyl ester solution)

·SR-399：Dipentaerythritol Pentaacrylate

·Byk 336：Modified dimethyl silicone copolymer (25 mass % dimethylbenzene/methoxy propyl acetate solution)

·Klucel M：Hydroxypropyl cellulose (the 2 mass % aqueous solution)

·ELVACITE 4026：High branch's polymethyl methacrylate (10 mass % 2- butanone solutions)

[chemical formula 12]

[chemical formula 13]

(preparations of particulate thermoplastic polymer aqueous dispersions)

Mixer, thermometer, dropping funel, nitrogen ingress pipe, reflux cooler are set to 1000ml 4 mouthfuls of flasks, imported Nitrogen carries out deoxidation, and adds polyethylene glycol monomethyl ether methacrylate (PEGMA, the average repeat unit of ethylene glycol Number：20) 10g, distilled water 200g and normal propyl alcohol 200g are heated to interior temperature as untill 70 DEG C.Then by the styrene of premixing (St) 10g, acrylonitrile (AN) 80g and 2,2 '-azodiisobutyronitrile 0.8g mixture were added dropwise through 1 hour.Completion of dropwise addition Intactly continue reaction 5 hours afterwards, add the 2 of 0.4g afterwards, 2 '-azodiisobutyronitrile, interior temperature is warming up to 80 DEG C.Connect , by the 2 of 0.5g, 2 '-azodiisobutyronitrile added through 6 hours.In total stage for having reacted 20 hours, polymerization enters Gone more than 98%, so as to obtained be by quality ratio PEGMA/St/AN=10/10/80 particulate thermoplastic polymer water Dispersion liquid.The particle diameter distribution of the particulate thermoplastic polymer has maximum in volume average particle size 150nm.

Here, particle diameter distribution is obtained as follows：The electron micrograph of polymer particles is shot, determines and amounts on photo The particle diameter of 5000 particulates, 50 parts will be divided into mark with logarithmic scale between the maximum of resulting particle size determination value to 0 Paint the frequency of occurrences of each particle diameter.In addition, on non-spherical particle, by with the particle area identical particle area on photo Spherical particle particle size values as particle diameter.

(making of original edition of lithographic printing plate 113)

In 40g/l sodium hydrate aqueous solution, thickness 0.19mm aluminium sheet is carried out into degreasing in 8 seconds with 60 DEG C of dippings, and Cleaned 2 seconds with desalted water.Then, using 15 seconds exchange the hydrochloric acid containing 12g/l and 38g/l aluminum sulfate (18 water and Thing) the aqueous solution in, by aluminium sheet with 33 DEG C of temperature and 130A/dm²Current density carried out Electrochemical roughening processing.With After desalted water cleans 2 seconds, aluminium sheet is etched 4 seconds by 155g/l aqueous sulfuric acid with 70 DEG C, thus decontaminated Processing, and cleaned with desalted water at 25 DEG C 2 seconds.In 155g/l aqueous sulfuric acid, by aluminium sheet with 45 DEG C of temperature And 22A/dm²Current density carry out the anodized of 13 seconds, cleaned 2 seconds with desalted water.Moreover, use 4g/l The PVPA aqueous solution handled 10 seconds at 40 DEG C, cleaned 2 seconds at 20 DEG C with desalted water, and dry and make Supporter.In supporter 2, surface roughness Ra is 0.21 μm, and anodic oxide coating amount is 4g/m²。

On a surface of supporter 2, above-mentioned back coating coating fluid (1) is subjected to rod painting, dried 120 seconds at 100 DEG C And form the back coating of 1.5 μm of thickness.

The image recording layer water class containing following particulate thermoplastic polymers, infrared absorbent and polyacrylic acid is prepared to apply Cloth liquid, pH is adjusted to 3.6 and is coated on afterwards on another surface of supporter 2,1 minute is dried at 50 DEG C to form image note Layer is recorded, so as to make original edition of lithographic printing plate 113.The dried coating weight of each composition described below.

Particulate thermoplastic polymer：0.7g/m²

Infrared absorbent IR-01：1.20×10^-4g/m²

Polyacrylic acid：0.09g/m²

Particulate thermoplastic polymer, infrared absorbent IR-01, polyacrylic acid used in image recording layer coating fluid As shown below.

Particulate thermoplastic polymer：Styrene/acrylonitrile copolymer (mol ratio 50/50), Tg：99 DEG C, the average grain of volume Footpath：60nm

Infrared absorbent IR-01：The infrared absorbent of following structures

[chemical formula 14]

Polyacrylic acid Mw：250,000

(making of original edition of lithographic printing plate 114)

Carrying out biaxial stretch-formed (draw ratio is longitudinal and transverse each 3.3 times) and the heat fixation of 3 minutes has been carried out at 240 DEG C After one surface of the polyethylene terephthalate film that 180 μm of thickness implements Corona discharge Treatment, rod applies above-mentioned back coating Coating fluid (1), dried 120 seconds at 100 DEG C and form the back coating of 1.5 μm of thickness.

8W/m is implemented on another surface of above-mentioned polyethylene terephthalate film²Corona discharge Treatment after, make Image record is formd with above-mentioned image recording layer coating fluid (1) and in a manner of the making identical with original edition of lithographic printing plate 1 Layer.

On above-mentioned image recording layer, using above-mentioned protective layer coating solution (1) and with the making with original edition of lithographic printing plate 1 Identical mode forms protective layer and has made original edition of lithographic printing plate 114.

(making of original edition of lithographic printing plate 115) (comparing use)

In the making of original edition of lithographic printing plate 101, the thickness of back coating is changed to 10 μm, in addition, with identical Mode form back coating and made original edition of lithographic printing plate 115.

(making of original edition of lithographic printing plate 116) (comparing use)

In the making of original edition of lithographic printing plate 109, the metal oxide in back coating coating fluid is changed to polyester tree Fat (KEMIT K-588 TORAY INDUSTRIES, INC. system, Tg：100 DEG C), in addition, the back of the body is formed in an identical manner Coating and made original edition of lithographic printing plate 116.

(making of original edition of lithographic printing plate 117) (comparing use)

In the making of original edition of lithographic printing plate 109, the metal oxide in back coating coating fluid is changed to acrylic acid Esters polymer latex (AE-337 JSR CORPORATION systems, Tg：- 30 DEG C), in addition, the back of the body is formed in an identical manner Coating and made original edition of lithographic printing plate 117.

(making of original edition of lithographic printing plate 118) (comparing use)

In the making of original edition of lithographic printing plate 114, the metal oxide in back coating coating fluid is changed to acrylic acid Esters polymer latex (AE-337 JSR CORPORATION systems, Tg：- 30 DEG C), in addition, the back of the body is formed in an identical manner Coating and made original edition of lithographic printing plate 118.

(making of original edition of lithographic printing plate 119) (comparing use)

In the making of original edition of lithographic printing plate 101, the particulate in back coating coating fluid is eliminated, in addition, with phase Same mode forms back coating and has made original edition of lithographic printing plate 119.

(making of original edition of lithographic printing plate 120) (comparing use)

In the making of original edition of lithographic printing plate 118, the particulate in back coating coating fluid is eliminated, in addition, with phase Same mode forms back coating and has made original edition of lithographic printing plate 120.

(making of original edition of lithographic printing plate 121) (comparing use)

In the making of original edition of lithographic printing plate 117, the particulate in back coating coating fluid is eliminated, in addition, with phase Same mode forms back coating and has made original edition of lithographic printing plate 121.

(evaluation of original edition of lithographic printing plate)

It is such as following that landing property, caking property, scratch, impression and Bake are put down on resulting each original edition of lithographic printing plate Slippery (Bekk smoothness) is evaluated.Evaluation result is shown in following table F.

The back side (back coating side) of original edition of lithographic printing plate is stood upward, is loading vertical 2cm × horizontal 2cm ethene thereon Propylene-diene rubbers (EDPM) piece, to nearby side stretching sheet rubber while applying 1kg load.Then, scanning electron is used Microscope (SEM) observes the back side of original edition of lithographic printing plate, and observes the regulation visual angle (200 300 μm of μ m) at 5 and determine The ratio of the particulate to come off.Evaluation is carried out according to following benchmark, and 3 be practical threshold level, and less than 2 are impermissible in practical It is horizontal.

5：The ratio of the particulate to come off is 0%.

4：The ratio of the particulate to come off is 0%, but the particulate that a part is not covered by back coating be present.

3：The ratio of the particulate to come off is more than 0% and less than 25%.

2：The ratio of the particulate to come off is more than 25% and less than 75%.

1：The ratio of the particulate to come off is more than 75% and less than 100%.

After the damping of 2 hours being carried out in the environment of 25 DEG C of 75%RH to 3 original edition of lithographic printing plate (10 × 10em), Stack gradually in the state of the sandwiching of linerless in the same direction and be used as layered product.Will with the brown paper with aluminium laminate layer The layered product packs, and in the state of 4kg load is applied, placed under 30 DEG C of environment 5 days.Then, lithographic plate is peeled off Printing plate precursor, and the bond state with the support body side surface of original edition of lithographic printing plate that detected by an unaided eye, the lithographic printing The support side of plate originals is adjacent with the image recording layer side surface of original edition of lithographic printing plate.Evaluation is entered according to following benchmark OK, 3 be practical threshold level, and less than 2 be the level being impermissible in practical.

5：Soap-free emulsion polymeization.

4：There is slight bonding.

3：There is a little bonding.

2：The strong bond peeled off reluctantly with hand if force.

1：Bond and be difficult the very strong bonding with hand stripping.

After the damping of 2 hours is carried out in the environment of 25 DEG C of 60%RH to original edition of lithographic printing plate, with 2.5cm × 2.5cm carries out punching press, and is installed on Shinto Scientific Co., Ltd.s continuous load type cut strength-testing machine TYPE (type)：18, connect with the surface of the original edition of lithographic printing plate of non-punching press and the back side of the original edition of lithographic printing plate of punching press Tactile mode is installed, and applies scratch to many places of original edition of lithographic printing plate with 500gf load.Abrasive lithographic plate will be applied Printing plate precursor is installed on Creo company system Trendsetter3244, with resolution ratio 2400dpi, output 7W, external drum rotating speed 150rpm, space of a whole page energy 110mJ/cm²Image exposure is carried out.Original edition of lithographic printing plate after image exposure is installed on TOKYO KIKAI SEIS AKUSHO, LTD. glue print cylinder press, and INKTEC is used with printing-ink as newpapers and periodicals CO., LTD. SOYBI KKST-S (red), and SAKATA INX CORPORATION. systems are used as fountain solution ECOSEVEN N-1, newpapers and periodicals paper is printed with the speed of 100,000/hour.In printing process, by the 1st, 000 printed article samples as sample, and detect by an unaided eye the degree that cut pollutes caused by scratch.Evaluation is according to following Benchmark is carried out, and 3 be practical threshold level, and less than 2 be the level being impermissible in practical.

5：No marking pollutes.

4：It can not confirm in visuognosis, but at presence 1 cut that the magnifying glass of 6 multiplying powers confirms can be used to pollute.

3：It can not confirm in visuognosis, but many places be present to be polluted with the cut that the magnifying glass of 6 multiplying powers confirms.

2：Exist in many places and can be polluted by visuognosis and the cut confirmed.

1：Cut pollution be present in entire surface.

In the environment of 25 DEG C of 60%RH, 10 original edition of lithographic printing plate (10cm × 65cm) are carried out with the damping of 2 hours Afterwards, stack gradually in the state of the sandwiching of linerless in the same direction and be used as layered product.With the ox with aluminium laminate layer Mulberry paper packs the layered product, and is clamped up and down with 5cm × 5cm stainless steel (SUS) plate, with the load as 500kgf Mode pressurizeed with vise.With the state pressurizeed, placed under 25 DEG C of environment 5 days.Then, to be commented with scratch Valency identical condition has carried out exposure, development, printing to original edition of lithographic printing plate.In printing process, by the 1st, 000 printing Thing samples as sample, and detected by an unaided eye the degree that cut pollutes caused by impression.Evaluation is entered according to following benchmark OK, 3 be practical threshold level, and less than 2 be the level being impermissible in practical.

5：It is pollution-free.

4：It can not confirm in visuognosis, but locally lie in and can be polluted with the cut that the magnifying glass of 6 multiplying powers confirms.

3：It can not confirm in visuognosis, but it is dirty in the presence of the cut that the magnifying glass of 6 multiplying powers confirms can be used in entire surface Dye.

2：Locally lying in being capable of the pollution arrived of visuognosis.

1：Existing in entire surface being capable of the pollution arrived of visuognosis.

The Bake smoothness on the original edition of lithographic printing plate back side (back coating surface) is determined according to JIS P8119 (1998). On measure, using KUMAGAI RIKI KOGYO Co., Ltd.s Bake smoothness testing machine, with the 1/10 of standard null tolerance That is 1ml air capacity is determined.From the viewpoint of the integrated displacement for preventing original edition of lithographic printing plate, Bake smoothness is excellent Elect less than 200 seconds, more preferably less than 100 seconds, more preferably less than 50 seconds as.

Each composition in table F used in described back coating is for example following.

Polyester resin 1：KEMIT K-588 TORAY INDUSTRIES, INC. system, (Tg：100℃)

Polymer emulsion 1：Acrylic polymer latex (AE-337 JSR CORPORATION systems, (Tg：-30℃)

Acrylic resin particle covered with silica：ART PEARL J-7P Negami Chemical Industrial Co., Ltd systems

Melmac particle covered with silica：OPTBEADS 6500M Nissan Chemical Industries, Ltd. system

Polyurethane resin particle covered with silica：ART PEARL C-800T Negami Chemical Industrial Co., Ltd systems

Acrylic resin particle：MX-500 Soken Chemical＆Engineering Co., Ltd.s system

Polyvinyl resin particle：CHEMIPEARL W200 Mitsui Chemicals, Inc. systems

Styrene resin beads：CHEMISNOW SX-500H Soken Chemical＆Engineering Co., Ltd. make

It is involved in the present invention to have comprising special metal oxide and specific particle it was found from the result shown in table F The original edition of lithographic printing plate of back coating is excellent in any one evaluation in landing property, caking property, scratch and impression, also, Even if linerless and be laminated, integrated displacement will not also occur.In addition, with the back coating for being unsatisfactory for important document involved in the present invention Comparative example any one evaluation in landing property, caking property, scratch, impression and integrated displacement of original edition of lithographic printing plate in It is insufficient.

[embodiment 201~207 and comparative example 201]

(making of original edition of lithographic printing plate 201~207)

In the making of original edition of lithographic printing plate 101, to the metal in back coating coating fluid as shown in following table G The species of oxide, the species of particulate, average grain diameter and the thickness of addition and back coating are changed, in addition, with Identical mode has made original edition of lithographic printing plate 201~207.

(making of original edition of lithographic printing plate 208) (comparing use)

In the making of original edition of lithographic printing plate 203, the thickness of back coating is changed to 3.5 μm, in addition, with identical Mode made original edition of lithographic printing plate 208.

(evaluation of original edition of lithographic printing plate)

On resulting each original edition of lithographic printing plate, in a manner of with the identical of embodiment 101 to landing property, caking property, Scratch and impression and Bake smoothness are evaluated.Evaluation result is shown in following table G.

Each composition in table G used in described back coating is for example following.

Silicon dioxide granule 1：SYLYSIA 440Fuji Silysia Chemical Ltd.

Silicon dioxide granule 2：SYLYSIA 436Fuji Silysia Chemical Ltd.

Silicon dioxide granule 3：SYLYSIA 320Fuji Silysia Chemical Ltd.

It is involved in the present invention to have comprising special metal oxide and specific particle it was found from the result shown in table G The original edition of lithographic printing plate of back coating is excellent in any one evaluation in landing property, caking property, scratch and impression, also, Even if linerless and be laminated, integrated displacement will not also occur.In addition, with the back coating for being unsatisfactory for important document involved in the present invention Comparative example any one evaluation in landing property, caking property, scratch, impression and integrated displacement of original edition of lithographic printing plate in It is insufficient.

[embodiment 301~302]

(making of original edition of lithographic printing plate 301)

The priming coat coating fluid (2) of following compositions is coated on to the system of original edition of lithographic printing plate 101 by bar coater Another surface (surface for not having back coating) of the supporter with back coating used in work, 30 have been dried at 90 DEG C Second.Coating weight is 10mg/m²。

(priming coat coating fluid (2))

High-molecular compound A (following structures) (matter average molecular weight：3 ten thousand) 0.05g

Methanol 27g

Ion exchange water 3g

[chemical formula 15]

The image recording layer coating fluid (3) of following compositions is coated on priming coat using bar coater.On drying, Carried out by warm-air type drying device at 115 DEG C 34 seconds.Dried overlay capacity is 1.4g/m²。

(image recording layer coating fluid (3))

[chemical formula 16]

[chemical formula 17]

On image recording layer, the protective layer coating solution (2) of following compositions is coated with bar coater, is done by warm-air type Dry device is dried 75 seconds at 125 DEG C and forms protective layer.Dried coating weight is 1.6g/m².In this way, make flat Lithographic printing plate master 301.

(making of original edition of lithographic printing plate 302)

The priming coat coating fluid (3) of following compositions is coated in the making of original edition of lithographic printing plate 101 with rod coater Another surface surface of back coating (do not have) of the used supporter with back coating, dried 15 seconds at 80 DEG C and It is 18mg/m to form dried coating weight²Priming coat.

(priming coat coating fluid (3))

High-molecular compound (following structures) 0.3g

Methanol 100g

[chemical formula 18]

On priming coat, 0.85g/m is turned into dried coating weight²Mode be coated with following compositions with rod coater Lower floor's coating fluid, dried 44 seconds at 160 DEG C, being cooled to the temperature of supporter under 17~20 DEG C of cold wind immediately turns into 35 DEG C and form lower floor.Then, 0.22g/m is turned into dried coating weight²Mode be coated with following compositions with rod coater Upper strata coating fluid, dried 25 seconds at 148 DEG C, and then gradually cooled down under 20~26 DEG C of wind and form upper strata.Such as This, has made original edition of lithographic printing plate 302.

(lower floor's coating fluid)

[chemical formula 19]

[chemical formula 20]

(upper strata coating fluid)

[chemical formula 21]

(evaluation of original edition of lithographic printing plate)

On resulting each original edition of lithographic printing plate, in a manner of with the identical of embodiment 101 to landing property, caking property, Scratch, impression and Bake smoothness are evaluated.Wherein, the image in scratch and the evaluation of impression has been carried out as described below Exposed and developed processing and printing.Show the result in following table H.

(image exposure)

Original edition of lithographic printing plate is arranged on Creo company system Trendsetter3244, with resolution ratio 2400dpi, output 7W, external drum rotating speed 150rpm, space of a whole page energy 110mJ/cm²Image exposure is carried out.

(development treatment)

Using Fujifilm Corporation automatic processing machine LP-1310HII, with transfer rate (linear velocity) 2m/ Minute, 30 DEG C of development temperature have carried out development treatment to the original edition of lithographic printing plate through image exposure.Developer solution uses Fujifilm Corporation DH-N 1: 4 water diluent, developer replenisher solution have used Fujifilm Corporation FCT-421 processed 1: 1.4 water diluent, retouching liquid have used Fujifilm Corporation HN-GV 1: 1 water to dilute Liquid.

(image exposure)

Original edition of lithographic printing plate is installed on Creo company system Trendsetter3244, with resolution ratio 2400dpi, output 7W, external drum rotating speed 150rpm, space of a whole page energy 110mJ/cm²Image exposure is carried out.

(development treatment)

Fujifilm Corporation developer solutions DT-2 is diluted with water to 1: 8 and is added to Fujifilm Corporation automatic processing machine LP-940HII, with 32 DEG C of development temperature, developing time 12 seconds to through image exposure Original edition of lithographic printing plate has carried out development treatment.

(printing)

Lithographic plate is installed on TOKYO KIKAI SEISAKUSHO, LTD. glue print cylinder press, as report Periodical uses INKTEC CO., LTD. SOYBI KKST-S (red) with printing-ink, and uses SAKATA as fountain solution INX CORPORATION. ECOSEVEN N-1, newpapers and periodicals paper is printed with the speed of 100,000/hour.

It is involved in the present invention to have comprising special metal oxide and specific particle it was found from the result shown in table H The development treatment type minus original edition of lithographic printing plate 301 and development treatment type eurymeric original edition of lithographic printing plate 302 of back coating are in cunning It is excellent in any one evaluation in falling property, caking property, scratch and impression, also, even if linerless and be laminated, will not also occur Integrated displacement.

[embodiment 401~402]

(making of the discarded plate originals 401 of printing)

In the making of original edition of lithographic printing plate 101, infrared absorbent is eliminated from image recording layer coating fluid (1) (1) printing, in addition, has been made in an identical manner with discarded plate originals 401.

(making of the discarded plate originals 402 of printing)

Tool priming coat coating fluid (4) rod of following compositions being applied to used in the making of original edition of lithographic printing plate 101 There is another surface (surface for not having back coating) of the supporter of back coating, dry 20 seconds and form dry at 100 DEG C Coating weight after dry is 20mg/m²Priming coat.

Polymer (following structures) 0.3 mass parts

The mass parts of pure water 60.0

The mass parts of methanol 939.7

[chemical formula 22]

On priming coat, rod applies the non-photosensitive layer coating fluid (1) of following compositions, is dried 60 seconds and shape at 100 DEG C It is 1.0mg/m into dried coating weight²Non-photosensitive layer.

(non-photosensitive layer coating fluid (1))

Above-mentioned binder polymer A is the condensation reaction thing (matter average molecular weight of 4 kinds of monomers of following (1)~(4)：85, 000, acid content：The 16 mass % solution of MFG/MEK=1/1 1.64meq/g).

On non-photosensitive layer, rod applies the hydrophilic layer coating fluid (1) of following compositions, is dried 75 seconds and shape at 125 DEG C It is 1.6mg/m into dried coating weight²Hydrophilic layer.In this way, printing has been made with discarded plate originals 402.

(hydrophilic layer coating fluid (1))

Above-mentioned Pluronic P-84 are ethylene oxide/propylene oxide block copolymer, and EMALEX710 is the polyoxyethylene moon Osmanthus ether.

(evaluations of the discarded plate originals of printing)

On resulting each printing with plate originals are discarded, to landing property, bonding in a manner of with the identical of embodiment 101 Property, scratch, impression and Bake smoothness are evaluated.But on printing with discarded plate originals 401, do not abraded and Image exposure in the evaluation of impression is just printed.Also, on printing with discarded plate originals 402, do not abraded and Image exposure in the evaluation of impression has just carried out following development treatments and printing.Evaluation result is shown in table I below.

(development treatment)

Using Fujifilm Corporation automatic processing machine LP-1310NewsII, with transfer rate (linear velocity) 2m/ minutes, 30 DEG C of development temperature have carried out development treatment to printing with discarded plate originals.Developer solution has used Fujifilm Corporation HN-D 1: 4 water diluent, developer replenisher solution have used FCT-421 1: 1.4 water diluent, retouch liquid Fujifilm Corporation HN-GV 1: 1 water diluent is used.

(printing)

Printing is installed on TOKYO KIKAI SEISAKUSHO, LTD. glue print cylinder press with discarded version, as Newpapers and periodicals use INKTEC CO., LTD. SOYBI KKST-S (red) with printing-ink, and use SAKATA as fountain solution INX CORPORATION. ECOSEVEN N-1, newpapers and periodicals paper is printed with the speed of 100,000/hour.

It is involved in the present invention to have comprising special metal oxide and specific particle it was found from the result shown in Table I On the machine of back coating developable printing with discarded plate originals 401 and the discarded plate originals 402 of development treatment type printing landing property, It is excellent in any one evaluation in caking property, scratch and impression, also, even if linerless and be laminated, will not also integrate Displacement.

[embodiment 501]

Above-mentioned original edition of lithographic printing plate 101 is carried out following image exposure, development treatment and made lithographic plate.

(image exposure)

(development treatment)

Development treatment has been carried out to the original edition of lithographic printing plate through image exposure using the automatic developing device 1 shown in Fig. 1. That is, in development treatment portion 10, carry out following process successively and made original edition of lithographic printing plate：Development treatment process, use Following developer solutions (A), remove the unexposed portion of image recording layer；Washing step, in washing portion 16 to the lithographic printing after development Version is washed；And desensitization chemical industry sequence, in desensitization processing unit 18 to the lithographic plate after washing using at following desensitizations Manage liquid.

Wherein, the automatic developing device 1 of one as automatic developing device is simply illustrated with reference to figure 1.

Automatic developing device 1 shown in Fig. 1 has development treatment portion 10, and with the transmission path along original edition of lithographic printing plate Development section 14, washing portion 16, desensitization processing unit 18 and the drying section 20 that the direction of transfer (arrow A) in footpath 12 is formed continuously.

Development section 14 is separated by outer side panel 111, and is provided with slit-shaped insert port 112 in outer side panel 111.

The developing trough 24 for being loaded with developer solution is provided with the inside of development section 14 and is printed to guiding lithographic plate inside developing trough 24 The insertion roller of brush plate originals is to 241.The shielded lid 242 in top of developing trough 24 covers.

Guide reel 143 and guide member, brush are set side by side with successively from direction of transfer upstream side in the inside of developing trough 24 Transfer roller 144, brush roll 142 and development section outlet roller 56 in roller 141, liquid.The lithographic plate being sent to inside developing trough 24 Master is impregnated in developer solution, and by removing non-image portion between the brush roll 141 of rotation, brush roll 142.

The lithographic plate to come is transported in washing portion 16 from developing trough 24, and washing water is supplied by washing sprayer 66, Washing removal is carried out to the developer solution for residuing in the space of a whole page etc., then in desensitization processing unit 18, passes through sol solution (desensitizationization processing Liquid) sprayer 72 is supplied to space of a whole page supply desensitization treatment fluid.

The dividing plate 201 being configured between development treatment portion 10 and drying section 20 is provided with slit-shaped insert mouth 202.And And the path between development treatment portion 10 and drying section 20 is provided with shutter (not shown), and original edition of lithographic printing plate does not pass through During path, path closes because of shutter.

Support roller 203, pipeline 204, transport roller pair 205, pipeline 206, transport roller pair 208 are sequentially provided with drying section 20. Slit pore is provided with the front end of pipeline 204, pipeline 205.Also, it is (warm to be provided with warm wind feed mechanism (not shown) in drying section 20 Wind supply part), heating mechanism (heat generating components) etc. drier (drying part).Outlet 209 is provided with drying section 20, and The lithographic plate dried by drier is discharged from outlet 209.

Add water and total amount is set to 100 mass %.(pH：9.4)

Condition in development treatment described below.

Developer temperatur：25℃

Transfer rate：100cm/min.

The brush rotating speed of development section：100rpm

The water supply conditions in washing portion：Water (25 DEG C, quantity delivered：10L/min)

Desensitization treatment fluid：Sol solution (FN-6, Fujifilm Corporation systems)/running water=1/1 (pH：3.5) Desensitization treatment fluid temperature：25 DEG C, pass through the desensitization processing liquid tank time：10L/min)

Industrial applicability

In accordance with the invention it is possible to a kind of printing original plate is provided, wherein when stacking comprising original edition of lithographic printing plate and is discarded During the printing original plate of plate originals, even if linerless, it can also prevent the mutual bonding of master integrated displacement, master, abrade this Three.Further, it is possible to provide a kind of layered product of above-mentioned printing original plate.

With reference to specific embodiment and the present invention is described in detail, but for those skilled in the art and Speech, in the case where not departing from the purpose and scope of the invention, it is obvious that can apply various changes or amendment.

The application is advocated based on Japanese patent application (Japanese patent application 2015- of on the June 30th, 2015 in Japanese publication Number 132081) priority, and be incorporated into using its content as reference in this specification.

Symbol description

1- automatic developing devices, 14- development treatments portion, 16- washings portion, 18- desensitization processing units.

Claims

1. a kind of printing original plate, its side on supporter has the layer containing polymer, and has in opposite side and contain The layer of metal oxide and particulate obtained from making organo-metallic compound or inorganic metal compound hydrolysis and polycondensation,

The average grain diameter of the particulate is more than 0.3 μm, also, the average grain diameter ratio of the particulate contains the metal oxide And the thickness of the layer of particulate is big.

2. printing original plate according to claim 1, wherein,

The particulate is the particulate with hydrophilic surface.

3. printing original plate according to claim 2, wherein,

The particulate with hydrophilic surface is selected from the organic resin particulate with hydrophilic surface, with hydrophilic surface At least one of inorganic particles.

4. printing original plate according to claim 3, wherein,

The organic resin particulate with hydrophilic surface is by selected from silica, aluminum oxide, titanium dioxide and zirconium oxide At least one of inorganic compound covering organic resin particulate.

5. the printing original plate according to claim 3 or 4, wherein,

The organic resin particulate with hydrophilic surface is the organic resin particulate covered by silica.

6. the printing original plate according to any one of claim 3 to 5, wherein,

The organic resin for forming the organic resin particulate with hydrophilic surface is selected from polyacrylics, poly- amino In formate ester resin, polystyrene resins, polyester resin, epoxylite, phenolic resinoid and melmac At least one resin.

7. printing original plate according to any one of claim 1 to 6, wherein,

The layer containing polymer is the eurymeric image recording layer containing infrared absorbent.

8. printing original plate according to any one of claim 1 to 6, wherein,

The layer containing polymer is the minus image note containing infrared absorbent, polymerization initiator, polymerizable compound Record layer.

9. printing original plate according to any one of claim 1 to 6, wherein,

The layer containing polymer is to contain infrared absorbent, polymerization initiator, polymerizable compound and microgranular high score The minus image recording layer of sub- compound.

10. printing original plate according to any one of claim 1 to 6, wherein,

The layer containing polymer is the minus image recording layer containing infrared absorbent and particulate thermoplastic polymer.

11. the printing original plate according to any one of claim 7 to 10, wherein,

The layer containing polymer can by printing-ink and fountain solution at least any one remove.

12. printing original plate according to any one of claim 1 to 6, wherein,

The layer containing polymer is non-photosensitive layer.

13. printing original plate according to claim 12, it is characterised in that

14. a kind of lithographic plate, its usage right requires the printing original plate any one of 1 to 11 and is made.

15. the discarded version of one kind printing, its usage right require the printing original plate described in 12 or 13 and are made.

16. a kind of layered product, it makes the printing original plate any one of claim 1 to 11 directly contact and be laminated multiple Form.

17. a kind of layered product, it makes the printing original plate described in claim 12 or 13 directly contact and be laminated multiple to form.

18. a kind of layered product, it makes the lithographic plate described in claim 14 directly contact and be laminated multiple to form.

19. a kind of layered product, it makes the printing described in claim 15 directly be contacted with discarded version and be laminated multiple to form.